Sheet for manufacturing semiconductor device, method for manufacturing sheet for manufacturing semiconductor device, and method for manufacturing semiconductor chip with film-like adhesive

Abstract

A semiconductor device manufacturing sheet comprising a substrate, a pressure sensitive adhesive layer, an intermediate layer and a film adhesive, wherein: the pressure sensitive adhesive layer, the intermediate layer and the film adhesive are laminated in said order on the substrate; the intermediate layer comprises, as the main ingredient, a non-silicon resin (β1) having a weight average molecular weight of 20,000-100,000; the film adhesive comprises a liquid ingredient (α2), or the pressure sensitive adhesive layer comprises a liquid ingredient (γ2); and H(βα)-H(β)>7% or H(βγ)-H(β)>7% is satisfied if the haze of a first test piece comprising the non-silicon resin (β1) and having a thickness of 10μm is represented by H(β), the haze of a second test piece comprising a mixture of the non-silicon resin (β1) and the ingredient (α2) and having a thickness of 10μm is represented by H(βα), and the haze of a third test piece comprising a mixture of the non-silicon resin (β1) and the ingredient (γ2) and having a thickness of 10μm is represented by H(βγ).

Description

[Technical field]

[0001] The present invention relates to a sheet for manufacturing a semiconductor device, a method for manufacturing the sheet for manufacturing a semiconductor device, and a method for manufacturing a semiconductor chip with a film-like adhesive. This application claims priority based on Japanese Patent Application No. 2020-058734, filed on March 27, 2020, the contents of which are incorporated herein by reference. [Background technology]

[0002] When manufacturing a semiconductor device, a semiconductor chip with a film-like adhesive is used, which includes a semiconductor chip and a film-like adhesive provided on the back surface of the semiconductor chip. An example of a method for producing a semiconductor chip with a film-like adhesive is shown below.

[0003] That is, first, a dicing die bonding sheet is attached to the back surface of a semiconductor wafer. The dicing die bonding sheet may, for example, be one that includes a support sheet and a film-like adhesive provided on one side of the support sheet, and the support sheet can be used as a dicing sheet. There are several types of support sheets with different configurations, such as one that includes a substrate and an adhesive layer provided on one side of the substrate, and one that consists of a substrate only. In the support sheet that includes an adhesive layer, the outermost surface on the adhesive layer side is the surface on which the film-like adhesive is provided. The dicing die bonding sheet is attached to the back side of the semiconductor wafer by the film-like adhesive therein.

[0004] Next, the semiconductor wafer and the film-like adhesive on the support sheet are both cut by blade dicing. The "cutting" of the semiconductor wafer is also called "splitting", and the semiconductor wafer is divided into individual semiconductor chips. The film-like adhesive is cut along the periphery of the semiconductor chip. This results in a semiconductor chip with a film-like adhesive, which includes a semiconductor chip and the cut film-like adhesive provided on the back surface of the semiconductor chip, and also results in a group of semiconductor chips with a film-like adhesive, which is configured by holding a plurality of these semiconductor chips with a film-like adhesive in an aligned state on the support sheet.

[0005] Next, the semiconductor chip with the film-like adhesive is peeled off from the support sheet and picked up. If a support sheet with a curable adhesive layer is used, the adhesive layer is cured at this time to reduce the adhesiveness, which makes picking up easier. In this manner, a semiconductor chip with a film-like adhesive for use in manufacturing a semiconductor device is obtained.

[0006] Another example of the method for producing a semiconductor chip with a film-like adhesive is shown below. That is, first, a backgrind tape (sometimes called a "surface protection tape") is applied to the circuit-forming surface of a semiconductor wafer. Next, a portion to be divided is set inside the semiconductor wafer, and a laser beam is irradiated so as to converge on the focal point, with the region included in this portion as a focal point, to form a modified layer inside the semiconductor wafer. Next, the back surface of the semiconductor wafer is ground using a grinder to adjust the thickness of the semiconductor wafer to a desired value, and the grinding force applied to the semiconductor wafer at this time is used to divide (single) the semiconductor wafer at the portion where the modified layer is formed, to produce a plurality of semiconductor chips. This method of dividing a semiconductor wafer with the formation of a modified layer is called stealth dicing (registered trademark), and is essentially completely different from laser dicing, which cuts the semiconductor wafer from its surface while irradiating the semiconductor wafer with laser light to scrape off the semiconductor wafer at the irradiated portion.

[0007] Next, one die bonding sheet is attached to the back surface (in other words, the ground surface) of all of these semiconductor chips fixed on the back grinding tape after the above-mentioned grinding. The die bonding sheet may be the same as the above-mentioned dicing die bonding sheet. In this way, the die bonding sheet may be designed to have the same configuration as the dicing die bonding sheet, but is not used during dicing of the semiconductor wafer. The die bonding sheet is also attached to the back surface of the semiconductor chip by the film-like adhesive therein.

[0008] Next, after removing the backgrind tape from the semiconductor chip, the die bonding sheet is stretched in a direction parallel to its surface (e.g., the surface of the film-like adhesive that is attached to the semiconductor chip) while being cooled, a process known as expanding (cool expanding), thereby cutting the film-like adhesive along the outer periphery of the semiconductor chip. By the above steps, a semiconductor chip with a film-like adhesive is obtained, which includes a semiconductor chip and the cut film-like adhesive provided on the back surface of the semiconductor chip.

[0009] Next, in the same manner as in the case where the above-mentioned blade dicing is used, the semiconductor chip with the film-like adhesive is separated from the support sheet and picked up, thereby obtaining a semiconductor chip with the film-like adhesive for use in manufacturing a semiconductor device.

[0010] Both the dicing die bonding sheet and the die bonding sheet can be used to manufacture a semiconductor chip with a film-like adhesive, and ultimately enable the manufacture of the desired semiconductor device. In this specification, the dicing die bonding sheet and the die bonding sheet are collectively referred to as "semiconductor device manufacturing sheet".

[0011] As a sheet for manufacturing a semiconductor device, for example, a dicing die bonding tape (corresponding to the dicing die bonding sheet) having a structure in which a base layer (corresponding to the support sheet) and an adhesive layer (corresponding to the film-like adhesive) are laminated in direct contact has been disclosed (see Patent Document 1). In this dicing die bonding tape, the 90-degree peel strength of the base layer and adhesive layer at -15°C is adjusted to a specific range, so that the adhesive layer can be accurately divided by expanding, and since the 90-degree peel strength of the base layer and adhesive layer at 23°C is adjusted to a specific range, when this dicing die bonding tape is used, a semiconductor chip with an adhesive layer (corresponding to the semiconductor chip with the film-like adhesive) can be picked up without difficulty, and peeling of the semiconductor wafer and the semiconductor chip from the adhesive layer can be suppressed during the process of picking up. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] Japanese Patent Application Publication No. 2018-56289 Summary of the Invention [Problem to be solved by the invention]

[0013] On the other hand, when the support sheet in the semiconductor device manufacturing sheet includes the base material and the adhesive layer, and the adhesive layer or the film-like adhesive contains a liquid component at room temperature, the liquid component may migrate between the adhesive layer and the film-like adhesive in the semiconductor device manufacturing sheet. If such migration occurs, either or both of the adhesive layer and the film-like adhesive will not be able to properly perform their functions. The dicing die bonding tape disclosed in Patent Document 1 does not include an adhesive layer.

[0014] The present invention aims to provide a sheet for manufacturing semiconductor device, which comprises a substrate, an adhesive layer, and a film-like adhesive, and in which even if the adhesive layer or the film-like adhesive contains a liquid component, migration of liquid components is suppressed between the adhesive layer and the film-like adhesive. [Means for solving the problem]

[0015] The present invention provides a film-like adhesive comprising a substrate, a pressure-sensitive adhesive layer, an intermediate layer, and a film-like adhesive, the pressure-sensitive adhesive layer, the intermediate layer, and the film-like adhesive being laminated in this order on the substrate, the intermediate layer containing a non-silicon-based resin (β1) having a weight average molecular weight of 20,000 to 100,000 as a main component, and further comprising at least one of a component (α2) and a component (γ2) which is liquid at a temperature of 23° C. and reacts with the main component contained in the film-like adhesive. the component (γ2) is liquid at a temperature of 23° C. and does not have a functional group that reacts with a main component contained in the pressure-sensitive adhesive layer; the haze of a first test piece in a film shape having a thickness of 10 μm and made of the non-silicon-based resin (β1) is H(β); and in the case where the film-like adhesive contains the component (α2), the haze of a second test piece in a film shape having a thickness of 10 μm and made of a mixture of 100 parts by mass of the non-silicon-based resin (β1) and 10 parts by mass of the component (α2) is H(βα), the H(βα) and H(β) can be calculated by the following formula (X1): (X1) H(βα)-H(β)>7% When the pressure-sensitive adhesive layer contains the component (γ2), when the haze of a film-like third test piece having a thickness of 10 μm and made of a mixture of 100 parts by mass of the non-silicon resin (β1) and 10 parts by mass of the component (γ2) is H(βγ), the H(βγ) and H(β) can be expressed by the following formula (X2): (X2) H(βγ)-H(β)>7% The present invention provides a sheet for manufacturing semiconductor device that satisfies the above requirements.

[0016] In the sheet for manufacturing semiconductor device of the present invention, the film-like adhesive may further contain, at least, a component (α1) that is solid at a temperature of 23°C as a main component, or the pressure-sensitive adhesive layer may contain, as a main component, a component (γ1) that is solid at a temperature of 23°C, and the component (α1) and the component (γ1) may be an acrylic resin having a structural unit derived from a (meth)acrylic acid ester. In the sheet for manufacturing a semiconductor device of the present invention, the intermediate layer may contain, as the non-silicon-based resin (β1), one or more resins selected from the group consisting of ethylene-vinyl acetate copolymers and polyolefins. In the sheet for manufacturing semiconductor device of the present invention, the intermediate layer may contain an ethylene-vinyl acetate copolymer as the non-silicon-based resin (β1), and in the ethylene-vinyl acetate copolymer, the ratio of the mass of structural units derived from vinyl acetate to the total mass of all structural units may be 30 mass% or less. The sheet for manufacturing semiconductor device of the present invention may be one for cutting the film-like adhesive by cooling and expanding the film-like adhesive.

[0017] The present invention provides a method for manufacturing a sheet for manufacturing a semiconductor device, the method comprising either or both of a film-like adhesive preparation step of preparing the film-like adhesive containing the component (α2) and an adhesive layer preparation step of preparing the adhesive layer containing the component (γ2).

[0018] The present invention provides a method for manufacturing a semiconductor chip with a film-like adhesive using the semiconductor device manufacturing sheet, the semiconductor chip with the film-like adhesive comprising a semiconductor chip and a film-like adhesive provided on the back surface of the semiconductor chip, the manufacturing method comprising the steps of: attaching the film-like adhesive in the sheet for manufacturing semiconductor device to the back surface of a semiconductor wafer while heating the sheet for manufacturing semiconductor device; cutting the semiconductor wafer to which the film-like adhesive has been attached across its entire thickness direction from the circuit formation surface side to divide the semiconductor chip, and cutting the sheet for manufacturing semiconductor device in its thickness direction from the film-like adhesive side to a region halfway through the intermediate layer to cut the film-like adhesive, but not cutting down to the pressure-sensitive adhesive layer, thereby obtaining a group of semiconductor chips with a film-like adhesive in which a plurality of the semiconductor chips with the film-like adhesive are aligned on the intermediate layer; and removing the semiconductor chip with the film-like adhesive from the intermediate layer and picking it up.

[0019] The present invention relates to a method for manufacturing a semiconductor chip with a film-like adhesive using the sheet for manufacturing a semiconductor device, the semiconductor chip with a film-like adhesive comprising a semiconductor chip and a film-like adhesive provided on the back surface of the semiconductor chip, and the manufacturing method includes a step of forming a modified layer inside the semiconductor wafer by irradiating a laser beam so as to be focused on a focal point set inside the semiconductor wafer, and a step of grinding the back surface of the semiconductor wafer after the modified layer is formed, and dividing the semiconductor wafer at the portion where the modified layer is formed by utilizing the force applied to the semiconductor wafer during grinding to obtain a group of semiconductor chips in a state in which a plurality of the semiconductor chips are aligned. the step of heating the semiconductor device manufacturing sheet while attaching the film-like adhesive thereto to the backsides of all of the semiconductor chips in the group of semiconductor chips; the step of cooling the semiconductor device manufacturing sheet after attachment to the semiconductor chips and stretching it in a direction parallel to its front surface while cooling the sheet to cut the film-like adhesive along the periphery of the semiconductor chips to obtain a group of semiconductor chips with film-like adhesive in which a plurality of the semiconductor chips with the film-like adhesive are aligned on the intermediate layer; and the step of separating the semiconductor chips with the film-like adhesive from the intermediate layer and picking them up. Effect of the Invention

[0020] According to the present invention, there is provided a sheet for manufacturing semiconductor device, which comprises a substrate, an adhesive layer, and a film-like adhesive, and in which even if the adhesive layer or the film-like adhesive contains a liquid component, migration of the liquid component is suppressed between the adhesive layer and the film-like adhesive. [Brief description of the drawings]

[0021] [Figure 1] 1 is a cross-sectional view that illustrates a schematic diagram of a sheet for manufacturing a semiconductor device according to one embodiment of the present invention. [Diagram 2] FIG. 2 is a plan view of the sheet for manufacturing semiconductor device shown in FIG. [Figure 3A]1A to 1C are cross-sectional views for illustrating a schematic example of a method for producing a semiconductor chip with a film-like adhesive according to an embodiment of the present invention. [Figure 3B] 1A to 1C are cross-sectional views for illustrating a schematic example of a method for producing a semiconductor chip with a film-like adhesive according to an embodiment of the present invention. [Figure 3C] 1A to 1C are cross-sectional views for illustrating a schematic example of a method for producing a semiconductor chip with a film-like adhesive according to an embodiment of the present invention. [Figure 4A] 1A to 1C are cross-sectional views for illustrating an example of a method for manufacturing a semiconductor chip. [Figure 4B] 1A to 1C are cross-sectional views for illustrating an example of a method for manufacturing a semiconductor chip. [Figure 4C] 1A to 1C are cross-sectional views for illustrating an example of a method for manufacturing a semiconductor chip. [Figure 5A] 10A to 10C are cross-sectional views for illustrating a schematic diagram of another example of a method for producing a semiconductor chip with a film-like adhesive according to one embodiment of the present invention. [Figure 5B] 10A to 10C are cross-sectional views for illustrating a schematic diagram of another example of a method for producing a semiconductor chip with a film-like adhesive according to one embodiment of the present invention. [Figure 5C] 10A to 10C are cross-sectional views for illustrating a schematic diagram of another example of a method for producing a semiconductor chip with a film-like adhesive according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] ◇ Sheets for manufacturing semiconductor devices A sheet for manufacturing semiconductor device according to one embodiment of the present invention comprises a substrate, a pressure-sensitive adhesive layer, an intermediate layer, and a film-like adhesive, and is configured by laminating the pressure-sensitive adhesive layer, the intermediate layer, and the film-like adhesive on the substrate in this order, the intermediate layer containing a non-silicon-based resin (β1) having a weight average molecular weight of 20,000 to 100,000 as a main component (sometimes simply referred to as "non-silicon-based resin (β1)" in this specification), and further, at least the film-like adhesive contains a component (α2) or the pressure-sensitive adhesive layer contains a component (γ2), and the component (α2) is in a liquid state at a temperature of 23°C. and has no functional group that reacts with the main component contained in the film-like adhesive, the component (γ2) is liquid at a temperature of 23° C. and has no functional group that reacts with the main component contained in the pressure-sensitive adhesive layer, and when the haze of a first test piece in a film shape having a thickness of 10 μm and made of the non-silicon-based resin (β1) is H(β), and when the film-like adhesive contains the component (α2), the haze of a second test piece in a film shape having a thickness of 10 μm and made of a mixture of 100 parts by mass of the non-silicon-based resin (β1) and 10 parts by mass of the component (α2) is H(βα), the H(βα) and H(β) can be calculated by the following formula (X1): (X1) H(βα)-H(β)>7% When the pressure-sensitive adhesive layer contains the component (γ2), when the haze of a film-like third test piece having a thickness of 10 μm and made of a mixture of 100 parts by mass of the non-silicon resin (β1) and 10 parts by mass of the component (γ2) is H(βγ), the H(βγ) and H(β) can be expressed by the following formula (X2): (X2) H(βγ)-H(β)>7% Meet the following.

[0023] Examples of the sheet for manufacturing semiconductor device in this embodiment include a sheet for manufacturing semiconductor device in which the intermediate layer contains the non-silicon resin (β1) as a main component, the film-like adhesive contains the component (α2), and the pressure-sensitive adhesive layer does not contain the component (γ2); a sheet for manufacturing semiconductor device in which the intermediate layer contains the non-silicon resin (β1) as a main component, the pressure-sensitive adhesive layer contains the component (γ2), and the film-like adhesive does not contain the component (α2); and a sheet for manufacturing semiconductor device in which the intermediate layer contains the non-silicon resin (β1) as a main component, the film-like adhesive contains the component (α2), and the pressure-sensitive adhesive layer contains the component (γ2).

[0024] In the sheet for manufacturing semiconductor device of this embodiment, when the film-like adhesive contains the component (α2), regardless of whether the pressure-sensitive adhesive layer contains the component (γ2), the H(βα) and H(β) satisfy the formula (X1). In such a sheet for manufacturing semiconductor device, it can be determined that the compatibility between the component (α2) and the non-silicon-based resin (β1) is low, and the migration of the component (α2) in the film-like adhesive to the intermediate layer is suppressed, and as a result, the migration of the component (α2) in the film-like adhesive to the pressure-sensitive adhesive layer is suppressed. On the other hand, in the sheet for manufacturing semiconductor device of this embodiment, when the pressure-sensitive adhesive layer contains the component (γ2), the H(βγ) and H(β) satisfy the formula (X2) regardless of whether the film-like adhesive contains the component (α2). In such a sheet for manufacturing semiconductor device, it can be determined that the compatibility between the component (γ2) and the non-silicon-based resin (β1) is low, and the migration of the component (γ2) in the pressure-sensitive adhesive layer to the intermediate layer is suppressed, and as a result, the migration of the component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive is suppressed. That is, in the sheet for manufacturing a semiconductor device of this embodiment, the intermediate layer functions as a layer for suppressing the migration of the component (α2) and the component (γ2).

[0025] In the sheet for producing semiconductor device of this embodiment, the effect of suppressing migration of the component (α2) in the film-like adhesive to the pressure-sensitive adhesive layer can be confirmed, for example, by the following method. That is, the semiconductor device manufacturing sheet is aged by being left stationary for a certain period of time under high temperature conditions, and the aged semiconductor device manufacturing sheet is used to produce a group of semiconductor chips with a film-like adhesive (e.g., a group of silicon chips with a film-like adhesive) in which a large number of semiconductor chips with a film-like adhesive are aligned and fixed on an intermediate layer in a laminated sheet by the film-like adhesive therein, by the method described below. Here, a "laminate sheet" refers to a laminate having a configuration in which a base material, a pressure-sensitive adhesive layer, and an intermediate layer are laminated in this order in the thickness direction. Then, the force required to peel the semiconductor chips with the film-like adhesive from the intermediate layer in the laminated sheet is measured, and this is used as the aged pick-up force of the semiconductor chips with the film-like adhesive. On the other hand, using a sheet for manufacturing semiconductor device that has not been aged (before aging), the force required to peel a semiconductor chip with a film-like adhesive from the intermediate layer in the laminated sheet is measured in a similar manner, and this is used as the unaged pick-up force of the semiconductor chip with a film-like adhesive. Furthermore, if there is no difference between the pick-up force of a semiconductor chip with a film-like adhesive with and without aging, or if there is a difference but the difference is extremely minor, it can be determined that no significant change has occurred in the composition of the film-like adhesive even when the sheet for manufacturing semiconductor device is aged, and that the sheet for manufacturing semiconductor device has the effect of suppressing the migration of component (α2) in the film-like adhesive to the adhesive layer.

[0026] In the sheet for manufacturing semiconductor device of this embodiment, the effect of suppressing the migration of component (γ2) in the adhesive layer to the film-like adhesive can be confirmed by the following method, for example, when component (γ2) is an antistatic agent. That is, in the same manner as above, the sheet for manufacturing semiconductor device is aged by being left to stand for a certain period of time under high temperature conditions, and the film-like adhesive is peeled off from the intermediate layer in the sheet for manufacturing semiconductor device after aging to prepare a test piece of the film-like adhesive. This test piece is left to stand for a certain period of time under conditions of constant temperature and relative humidity (for example, temperature 23°C, relative humidity 50%) to condition the humidity, and then the surface resistivity of the exposed surface of the film-like adhesive that was the intermediate layer side after this humidity conditioning is measured, and this is adopted as the aged surface resistivity of the film-like adhesive. On the other hand, using a sheet for manufacturing semiconductor device that has not been aged (before aging), the surface resistivity of the exposed surface that was the intermediate layer side of the film-like adhesive is measured in the same manner, and this is used as the surface resistivity of the film-like adhesive without aging. If there is no difference (more specifically, a decrease) between the surface resistivity of the film-like adhesive with and without aging, or if there is a difference but the degree of difference is extremely minor, it can be determined that no significant change has occurred in the composition of the adhesive layer containing the antistatic agent even when the sheet for manufacturing semiconductor device is aged, and that the sheet for manufacturing semiconductor device has the effect of suppressing the migration of the component (γ2) in the adhesive layer to the film-like adhesive. When component (γ2) is a component other than an antistatic agent, for example, if the physical properties of the adhesive layer reflecting the presence of that component do not differ depending on whether the adhesive layer has aged or not, or if a difference is observed but the degree of difference is extremely minor, then it can be determined that the sheet for manufacturing semiconductor device has the effect of suppressing the migration of component (γ2) in the adhesive layer to the film-like adhesive.

[0027] In this specification, the term "main component" does not necessarily mean the non-silicon-based resin (β1) in the intermediate layer described above, but refers to the component whose content (parts by mass) is the largest in a layer (film) containing that component, and whose weight average molecular weight is 20,000 or more. For example, in the intermediate layer, the content (parts by mass) of the non-silicon-based resin (β1) is the largest among all the components, and the weight average molecular weight of the non-silicon-based resin (β1) is 20,000 or more.

[0028] In this specification, components that are liquid at a temperature of 23° C., such as the component (α2) and the component (γ2), may be collectively referred to simply as “liquid components”.

[0029] The first test piece, the second test piece and the third test piece are all in the form of a film having a thickness of 10 μm, and the overall shape thereof is not particularly limited as long as the haze can be measured, for example.

[0030] In this specification, the "thickness" is not limited to the first to third test pieces, and unless otherwise specified, it means the average thickness measured at five randomly selected points on the object, and can be obtained using a constant pressure thickness gauge in accordance with JIS K7130.

[0031] The H(β), H(βα) and H(βγ) can all be measured in accordance with JIS K 7136:2000.

[0032] The H(β) is not particularly limited as long as it satisfies the formulae (X1) and (X2). H(β) may be, for example, any one of 0.1 to 20%, 1 to 18%, and 2 to 15%, in that the intermediate layer can be formed more easily.

[0033] The first test piece can be produced by preparing a first test composition containing the non-silicon resin (β1) and a solvent, applying the first test composition to a surface to be formed of the first test piece, and drying the composition. The surface to be formed of the first test piece can be, for example, a release-treated surface of a release film.

[0034] The first test piece is made of a non-silicon-based resin (β1). The first test piece contains only the non-silicon-based resin (β1) as a constituent component, or contains impurities other than the non-silicon-based resin (β1), but the amount of impurities is so small that it does not change the physical properties of the first test piece, and the first test piece can be considered to contain substantially only the non-silicon-based resin (β1). For example, the ratio of the content of the non-silicon-based resin (β1) in the first test piece to the total mass of the first test piece may be 99 mass% or more.

[0035] The H(βα) is not particularly limited as long as it satisfies the formula (X1). H(βα) may be, for example, any one of 8 to 80%, 10 to 75%, and 12 to 70%, in that it is easier to form an intermediate layer and a film-like adhesive.

[0036] The second test piece can be produced by preparing a second test composition containing the non-silicon resin (β1), the component (α2), and a solvent, applying the second test composition to the target surface of the second test piece, and drying the composition. The target surface of the second test piece is the same as the target surface of the first test piece described above. In the second test composition, it is preferable that the components are mixed uniformly, and by doing so, the second test piece can be prepared with the components mixed uniformly, and H(βα) can be measured with higher accuracy. For this purpose, when preparing the second test composition, all the components are mixed together and then thoroughly stirred by a known method.

[0037] The second test piece is composed of a mixture of 100 parts by mass of a non-silicon-based resin (β1) and 10 parts by mass of a component (α2). The second test piece contains only the non-silicon-based resin (β1) and the component (α2) as its constituent components, or contains impurities other than the non-silicon-based resin (β1) and the component (α2), but the amount of impurities is so small that it does not change the physical properties of the second test piece, and it can be considered that the second test piece substantially contains only the non-silicon-based resin (β1) and the component (α2). For example, the ratio of the total content of the non-silicon-based resin (β1) and the component (α2) to the total mass of the second test piece in the second test piece may be 99% by mass or more.

[0038] The H(βγ) is not particularly limited as long as it satisfies the formula (X2). H(βγ) may be, for example, any one of 8 to 80%, 10 to 75%, and 12 to 70%, in that the intermediate layer and the pressure-sensitive adhesive layer can be formed more easily.

[0039] The third test piece can be produced by preparing a third test composition containing the non-silicon resin (β1), the component (γ2), and a solvent, applying the third test composition to a target surface of the third test piece, and drying the composition. The target surface of the third test piece is the same as the target surface of the first test piece described above. In the third test composition, it is preferable that the components are mixed uniformly, and by doing so, the third test piece can be prepared with the components mixed uniformly, and H(βγ) can be measured with higher accuracy. For this purpose, when preparing the third test composition, all the components are mixed together and then thoroughly stirred by a known method.

[0040] The third test piece is composed of a mixture of 100 parts by mass of a non-silicon resin (β1) and 10 parts by mass of component (γ2). The third test piece contains only the non-silicon resin (β1) and component (γ2) as its constituent components, or contains impurities in addition to the non-silicon resin (β1) and component (γ2), but the content of the impurities is a trace amount that does not change the physical properties of the third test piece, and it can be regarded as substantially containing only the non-silicon resin (β1) and component (γ2). For example, the ratio of the total content of the non-silicon resin (β1) and component (γ2) to the total mass of the third test piece in the third test piece may be 99% by mass or more.

[0041] The above H(βα) - H(β) may be more than 7%, but in terms of further suppressing the migration of component (α2) in the film adhesive to the adhesive layer, it is preferably 7.5% or more, and for example, it may be either 9% or more, and 11% or more. The upper limit value of H(βα) - H(β) is not particularly limited. In terms of easily forming the film adhesive and the intermediate layer that satisfy the above formula (X1), H(βα) - H(β) is preferably 90% or less. H(βα) - H(β) is preferably, for example, more than 7% and 90% or less (7% < H(βα) - H(β) ≤ 90%), and may be any one of 7.5 - 90%, 9 - 90%, and 11 - 90%.

[0042] The above H(βγ) - H(β) may be more than 7%, but in terms of further suppressing the migration of component (γ2) in the adhesive layer to the film adhesive, it is preferably 7.5% or more, and for example, it may be either 9% or more, and 11% or more. The upper limit value of H(βγ) - H(β) is not particularly limited. In terms of easily forming the adhesive layer and the intermediate layer that satisfy the above formula (X2), H(βγ) - H(β) is preferably 90% or less. H(βγ) - H(β) is preferably, for example, more than 7% and 90% or less (7% < H(βγ) - H(β) ≤ 90%), and may be any one of 7.5 - 90%, 9 - 90%, and 11 - 90%.

[0043] When the semiconductor device manufacturing sheet of this embodiment is used as a dicing die bonding sheet and blade dicing is performed, the semiconductor device manufacturing sheet has the intermediate layer, which makes it easy to prevent the blade from reaching the substrate, and suppresses the generation of whisker-like cutting debris (also known as whiskers, hereinafter, not limited to those derived from the substrate, but simply referred to as "cutting debris") from the substrate. Furthermore, since the main component of the intermediate layer cut by the blade is a non-silicon-based resin (β1) having a weight average molecular weight of 20,000 to 100,000, and in particular, the weight average molecular weight is 100,000 or less, the generation of the cutting debris from the intermediate layer can also be suppressed.

[0044] On the other hand, when the semiconductor device manufacturing sheet of this embodiment is used as a die bonding sheet and dicing involving the formation of a modified layer on a semiconductor wafer (stealth dicing (registered trademark)) is performed, since the semiconductor device manufacturing sheet has the intermediate layer, the semiconductor device manufacturing sheet can be subsequently stretched in a direction parallel to its surface (for example, the surface of the film-like adhesive that is attached to the semiconductor chip), i.e., expanded, so that the film-like adhesive can be cut accurately at the desired location and cutting defects can be suppressed.

[0045] In this way, the sheet for manufacturing semiconductor device of this embodiment can be imparted with properties that suppress the occurrence of defects when dividing semiconductor wafers, such as suppressing the generation of cutting chips from the base material and intermediate layer during blade dicing, and suppressing poor cutting of the film-like adhesive during the expanding process, and can be made to have excellent suitability for dividing semiconductor wafers.

[0046] In this specification, unless otherwise specified, the "weight average molecular weight" is a polystyrene equivalent value measured by gel permeation chromatography (GPC).

[0047] The method of using the sheet for manufacturing semiconductor device of this embodiment will be described in detail later.

[0048] The sheet for manufacturing a semiconductor device according to the present embodiment will be described in detail below with reference to the drawings. Note that the drawings used in the following description may show the main parts enlarged for the sake of convenience in order to make the features of the present invention easier to understand, and the dimensional ratios of each component may not necessarily be the same as the actual ones.

[0049] FIG. 1 is a cross-sectional view that illustrates a sheet for manufacturing a semiconductor device according to one embodiment of the present invention, and FIG. 2 is a plan view of the sheet for manufacturing a semiconductor device illustrated in FIG. In FIG. 2 and subsequent figures, the same components as those shown in the figures already described are given the same reference numerals as in the figures already described, and detailed description thereof will be omitted.

[0050] The sheet 101 for manufacturing semiconductor device shown here includes a base material 11, and is configured by laminating, in this order, a pressure-sensitive adhesive layer 12, an intermediate layer 13, and a film-like adhesive 14 on the base material 11. The sheet 101 for manufacturing semiconductor device further includes a release film 15 on a surface 14a (hereinafter sometimes referred to as a "first surface") of the film-like adhesive 14 opposite to the side on which the intermediate layer 13 is provided.

[0051] In the sheet 101 for manufacturing semiconductor device, an adhesive layer 12 is provided on one surface (sometimes referred to as the "first surface" in this specification) 11a of a substrate 11, an intermediate layer 13 is provided on a surface (sometimes referred to as the "first surface" in this specification) 12a of the adhesive layer 12 opposite to the side on which the substrate 11 is provided, a film-like adhesive 14 is provided on a surface (sometimes referred to as the "first surface" in this specification) 13a of the intermediate layer 13 opposite to the side on which the adhesive layer 12 is provided, and a release film 15 is provided on the first surface 14a of the film-like adhesive 14. In this manner, the sheet 101 for manufacturing semiconductor device is configured by laminating the substrate 11, the adhesive layer 12, the intermediate layer 13, and the film-like adhesive 14 in this order in the thickness direction.

[0052] When the semiconductor device manufacturing sheet 101 is used, with the release film 15 removed, the first surface 14a of the film-like adhesive 14 therein is affixed to the back surface of a semiconductor wafer, a semiconductor chip, or a semiconductor wafer that has not been completely divided (not shown).

[0053] In this specification, for both a semiconductor wafer and a semiconductor chip, the surface on which circuits are formed is referred to as the "circuit-forming surface," and the surface opposite the circuit-forming surface is referred to as the "rear surface."

[0054] In this specification, a laminate having a structure in which a base material and a pressure-sensitive adhesive layer are laminated in their thickness direction and no intermediate layer is laminated may be referred to as a "support sheet." In Figure 1, the support sheet is indicated by the reference numeral 1. A laminate having a structure in which a substrate, a pressure-sensitive adhesive layer, and an intermediate layer are laminated in this order in the thickness direction may be referred to as a "laminate sheet." In Fig. 1, the laminate sheet is indicated by the reference numeral 10. The laminate of the support sheet and the intermediate layer is included in the laminate sheet.

[0055] When viewed from above, the intermediate layer 13 and the film-like adhesive 14 each have a circular planar shape, and the diameter of the intermediate layer 13 and the diameter of the film-like adhesive 14 are the same. In the semiconductor device manufacturing sheet 101, the intermediate layer 13 and the film-like adhesive 14 are arranged so that their centers coincide, in other words, so that the positions of the outer periphery of the intermediate layer 13 and the film-like adhesive 14 both coincide in the radial direction.

[0056] The first surface 13a of the intermediate layer 13 and the first surface 14a of the film-like adhesive 14 each have an area smaller than that of the first surface 12a of the pressure-sensitive adhesive layer 12. 13 (i.e., diameter) and the width W of the film adhesive 14 14The maximum values ​​(i.e., diameters) of are both smaller than the maximum width of the adhesive layer 12 and the maximum width of the base material 11. Therefore, in the sheet 101 for manufacturing semiconductor device, a part of the first surface 12a of the adhesive layer 12 is not covered by the intermediate layer 13 and the film-like adhesive 14. In such an area of ​​the first surface 12a of the adhesive layer 12 where the intermediate layer 13 and the film-like adhesive 14 are not laminated, the release film 15 is laminated in direct contact therewith, and when the release film 15 is removed, this area is exposed (hereinafter, in this specification, this area may be referred to as the "non-laminated area"). In addition, in the semiconductor device manufacturing sheet 101 having a release film 15, the areas of the adhesive layer 12 that are not covered by the intermediate layer 13 and the film-like adhesive 14 may or may not have areas where the release film 15 is not laminated, as shown here.

[0057] The semiconductor device manufacturing sheet 101, in which the film-like adhesive 14 is not cut and is attached to the semiconductor wafer or semiconductor chip or the like by the film-like adhesive 14, can be fixed by attaching a part of the non-laminated region of the pressure-sensitive adhesive layer 12 therein to a jig such as a ring frame for fixing a semiconductor wafer. Therefore, it is not necessary to provide a separate jig adhesive layer on the semiconductor device manufacturing sheet 101 for fixing the semiconductor device manufacturing sheet 101 to the jig. And since it is not necessary to provide a jig adhesive layer, the semiconductor device manufacturing sheet 101 can be manufactured inexpensively and efficiently.

[0058] Thus, the sheet 101 for manufacturing semiconductor device has an advantageous effect by not including a jig adhesive layer, but may include a jig adhesive layer. In this case, the jig adhesive layer is provided in a region near the periphery of the surface of any of the layers constituting the sheet 101 for manufacturing semiconductor device. Examples of such a region include the non-laminated region on the first surface 12a of the pressure-sensitive adhesive layer 12.

[0059] The adhesive layer for the jig may be a known one, for example, it may be a single-layer structure containing an adhesive component, or it may be a multi-layer structure in which layers containing an adhesive component are laminated on both sides of a core sheet.

[0060] Furthermore, as described below, when the semiconductor device manufacturing sheet 101 is stretched in a direction parallel to its surface (for example, the first surface 12a of the adhesive layer 12), that is, so-called expanding, the presence of the non-laminated region on the first surface 12a of the adhesive layer 12 makes it easy to expand the semiconductor device manufacturing sheet 101. Not only can the film-like adhesive 14 be easily cut, but peeling of the intermediate layer 13 and the film-like adhesive 14 from the adhesive layer 12 can also be suppressed.

[0061] In the sheet 101 for manufacturing semiconductor device, the intermediate layer 13 contains a non-silicon based resin (β1) having a weight average molecular weight of 20,000 to 100,000 as a main component.

[0062] The sheet for manufacturing a semiconductor device of this embodiment is not limited to that shown in Figures 1 and 2, and some of the configurations shown in Figures 1 and 2 may be changed, deleted, or added within the scope that does not impair the effects of the present invention.

[0063] For example, the sheet for manufacturing a semiconductor device of this embodiment may include other layers that do not fall under any of the following: a substrate, a pressure-sensitive adhesive layer, an intermediate layer, a film-like adhesive, a release film, and a jig adhesive layer. However, the sheet for manufacturing a semiconductor device of this embodiment preferably includes the pressure-sensitive adhesive layer in direct contact with the substrate, the intermediate layer in direct contact with the pressure-sensitive adhesive layer, and the film-like adhesive in direct contact with the intermediate layer, as shown in FIG.

[0064] For example, in the sheet for manufacturing semiconductor device of this embodiment, the planar shapes of the intermediate layer and the film-like adhesive may be shapes other than circular, and the planar shapes of the intermediate layer and the film-like adhesive may be the same as or different from each other. Furthermore, the area of ​​the first surface of the intermediate layer and the area of ​​the first surface of the film-like adhesive are both preferably smaller than the area of ​​the surface of the layer closer to the substrate than these (e.g., the first surface of the pressure-sensitive adhesive layer), and may be the same as or different from each other. Furthermore, the positions of the outer peripheries of the intermediate layer and the film-like adhesive may or may not coincide in the radial direction. Next, each layer constituting the sheet for manufacturing semiconductor device of this embodiment will be described in more detail.

[0065] ○Base material The substrate is in the form of a sheet or film. The material constituting the substrate is preferably various resins, and specific examples thereof include polyethylene (low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE, etc.)), polypropylene (PP), polybutene, polybutadiene, polymethylpentene, styrene-ethylenebutylene-styrene block copolymer, polyvinyl chloride, vinyl chloride copolymer, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyurethane, polyurethane acrylate, polyimide (PI), ionomer resin, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, ethylene copolymers other than ethylene-(meth)acrylic acid copolymer and ethylene-(meth)acrylic acid ester copolymer, polystyrene, polycarbonate, fluororesin, water additives, modified products, crosslinked products, or copolymers of any of these resins, and the like.

[0066] In this specification, the term "(meth)acrylic acid" is a concept that includes both "acrylic acid" and "methacrylic acid." The same applies to terms similar to (meth)acrylic acid. For example, "(meth)acrylate" is a concept that includes both "acrylate" and "methacrylate," and "(meth)acryloyl group" is a concept that includes both "acryloyl group" and "methacryloyl group."

[0067] The resin constituting the substrate may be of only one type, or of two or more types. When two or more types are used, the combination and ratio thereof can be selected arbitrarily.

[0068] The substrate may be one layer (single layer) or two or more layers. When the substrate is made of multiple layers, these layers may be the same or different from each other, and the combination of these layers is not particularly limited as long as it does not impair the effects of the present invention. In this specification, not only in the case of a substrate, "multiple layers may be the same or different from one another" means "all layers may be the same, all layers may be different, or only some layers may be the same", and further, "multiple layers are different from one another" means "at least one of the constituent materials and thicknesses of each layer is different from one another".

[0069] The thickness of the substrate can be appropriately selected depending on the purpose, but is preferably 50 to 300 μm, and more preferably 60 to 150 μm. When the thickness of the substrate is equal to or greater than the lower limit, the structure of the substrate is more stable. When the thickness of the substrate is equal to or less than the upper limit, the film-like adhesive can be cut more easily during blade dicing and the expansion of the sheet for manufacturing semiconductor device (film-like adhesive). Here, the "thickness of the substrate" means the thickness of the entire substrate. For example, the thickness of a substrate consisting of multiple layers means the total thickness of all layers constituting the substrate.

[0070] In order to improve adhesion to other layers, such as an adhesive layer, provided thereon, the substrate may be subjected to a surface treatment such as sandblasting, solvent treatment, embossing, or other roughening treatment; or a corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone / ultraviolet radiation treatment, flame treatment, chromate treatment, hot air treatment, or other oxidation treatment. The surface of the substrate may be treated with a primer. The substrate may have an antistatic coating layer; a layer that prevents the substrate from adhering to other sheets or to an adsorption table when the die bonding sheets are stacked and stored; or the like.

[0071] In addition to the main constituent materials such as the resin, the substrate may contain various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers).

[0072] The optical properties of the substrate are not particularly limited as long as the effects of the present invention are not impaired. The substrate may be, for example, a substrate that transmits laser light or energy rays.

[0073] The substrate can be produced by a known method. For example, a substrate containing a resin (having a resin as a constituent material) can be produced by molding the resin or a resin composition containing the resin.

[0074] Adhesive layer The pressure-sensitive adhesive layer is in the form of a sheet or film and contains a pressure-sensitive adhesive as a main component. The pressure-sensitive adhesive as a main component has a weight-average molecular weight of 20,000 or more. The component with the largest content (parts by mass) in the pressure-sensitive adhesive layer is the pressure-sensitive adhesive as a main component.

[0075] The adhesive layer may or may not contain the component (γ2) in addition to the adhesive. The adhesive layer may or may not contain, as the main component (adhesive), a component (γ1) that is solid at a temperature of 23° C. When the component (γ1) is the main component (adhesive), the weight average molecular weight of component (γ1) is 20,000 or more, and the component that is the maximum in content (parts by mass) in the adhesive layer is component (γ1).

[0076] The pressure-sensitive adhesive layer preferably contains the component (γ1), and may contain both component (γ1) and component (γ2), or may contain component (γ1) but not component (γ2).

[0077] The adhesive layer can be formed using an adhesive composition containing the adhesive and, if necessary, a component (γ2). For example, the adhesive composition can be applied to a surface on which the adhesive layer is to be formed, and then dried as necessary to form the adhesive layer at the desired site. The ratio of the contents of the components that do not vaporize at room temperature in the pressure-sensitive adhesive composition is usually the same as the ratio of the contents of the components in the pressure-sensitive adhesive layer. In this specification, "room temperature" means a temperature that is not particularly cooled or heated, that is, an ordinary temperature, and examples of the temperature include a temperature of 15 to 25°C.

[0078] In the pressure-sensitive adhesive layer, the proportion of the total content of one or more ingredients contained in the pressure-sensitive adhesive layer, which will be described later, relative to the total mass of the pressure-sensitive adhesive layer does not exceed 100 mass %. Similarly, in the pressure-sensitive adhesive composition, the proportion of the total content of one or more components contained in the pressure-sensitive adhesive composition, which will be described later, relative to the total mass of the pressure-sensitive adhesive composition does not exceed 100 mass %.

[0079] The pressure-sensitive adhesive composition may be applied by a known method, for example, a method using various coaters such as an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, a screen coater, a Mayer bar coater, or a kiss coater.

[0080] The drying conditions for the pressure-sensitive adhesive composition are not particularly limited. When the pressure-sensitive adhesive composition contains a solvent described below, it is preferable to heat-dry the composition. In this case, it is preferable to dry the composition at 70 to 130°C for 10 seconds to 5 minutes.

[0081] Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber-based resins, silicone resins, epoxy-based resins, polyvinyl ethers, polycarbonates, and ester-based resins, with acrylic resins being preferred.

[0082] When the pressure-sensitive adhesive layer contains component (γ1) as the main component (pressure-sensitive adhesive), component (γ1) is preferably an acrylic resin having a structural unit derived from a (meth)acrylic acid ester.

[0083] In this specification, the term "adhesive resin" includes both a resin having adhesiveness and a resin having adhesiveness. For example, the adhesive resin includes not only resins that are adhesive by themselves, but also resins that exhibit adhesiveness when used in combination with other components such as additives, and resins that exhibit adhesiveness in the presence of a trigger such as heat or water.

[0084] The pressure-sensitive adhesive layer may be either curable or non-curable, for example, either energy ray curable or non-energy ray curable. The physical properties of the curable pressure-sensitive adhesive layer before and after curing can be easily adjusted.

[0085] In this specification, the term "energy rays" refers to electromagnetic waves or charged particle beams that have an energy quantum. Examples of energy rays include ultraviolet rays, radiation, and electron beams. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, or an LED lamp as an ultraviolet ray source. Electron beams can be irradiated by generating them using an electron beam accelerator or the like. In this specification, the term "energy ray curable" means a property of being cured by irradiation with energy rays, and the term "non-energy ray curable" means a property of not being cured even when irradiated with energy rays.

[0086] The adhesive layer may consist of one layer (single layer), or may consist of two or more layers. If it consists of multiple layers, these multiple layers may be the same or different, and the combination of these multiple layers is not particularly limited.

[0087] The thickness of the pressure-sensitive adhesive layer is preferably from 1 to 100 μm, more preferably from 1 to 60 μm, and particularly preferably from 1 to 30 μm. Here, "the thickness of the adhesive layer" means the thickness of the entire adhesive layer, and for example, the thickness of an adhesive layer consisting of multiple layers means the total thickness of all layers that make up the adhesive layer.

[0088] The optical properties of the pressure-sensitive adhesive layer are not particularly limited as long as the effects of the present invention are not impaired. For example, the pressure-sensitive adhesive layer may transmit energy rays. Next, the pressure-sensitive adhesive composition will be described.

[0089] <<Adhesive composition>> When the adhesive layer is energy ray curable, examples of the adhesive composition containing an energy ray curable adhesive, i.e., the energy ray curable adhesive composition, include an adhesive composition (I-1) containing a non-energy ray curable adhesive resin (I-1a) (hereinafter may be abbreviated as "adhesive resin (I-1a)") and an energy ray curable compound; an adhesive composition (I-2) containing an energy ray curable adhesive resin (I-2a) (hereinafter may be abbreviated as "adhesive resin (I-2a)") in which an unsaturated group has been introduced into the side chain of the non-energy ray curable adhesive resin (I-1a); an adhesive composition (I-3) containing the adhesive resin (I-2a) and an energy ray curable compound, and the like.

[0090] The pressure-sensitive adhesive compositions (I-1), (I-2) and (I-3) may or may not further contain the component (γ2). The pressure-sensitive adhesive compositions (I-1), (I-2) and (I-3) may or may not further contain the component (γ1) as the main component (pressure-sensitive adhesive). The pressure-sensitive adhesive compositions (I-1), (I-2) and (I-3) each preferably contain component (γ1), and may contain both component (γ1) and component (γ2), or may contain component (γ1) but not component (γ2).

[0091] <Adhesive composition (I-1)> As described above, the pressure-sensitive adhesive composition (I-1) contains a non-energy ray-curable pressure-sensitive adhesive resin (I-1a) and an energy ray-curable compound, and may or may not further contain the component (γ2). In the adhesive composition (I-1), the adhesive resin (I-1a) or the energy ray curable compound may be component (γ1), or the adhesive resin (I-1a) or the energy ray curable compound may be the main component.

[0092] [Adhesive resin (I-1a)] The adhesive resin (I-1a) is preferably an acrylic resin. The acrylic resin may, for example, be an acrylic polymer having at least a structural unit derived from an alkyl (meth)acrylate ester. The structural unit contained in the acrylic resin may be of only one type, or of two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0093] The adhesive composition (I-1) may contain only one type of adhesive resin (I-1a), or two or more types. When two or more types are contained, the combination and ratio thereof can be selected arbitrarily.

[0094] In the pressure-sensitive adhesive composition (I-1), the content of the adhesive resin (I-1a) relative to the total mass of the pressure-sensitive adhesive composition (I-1) is preferably 5 to 99 mass%, more preferably 10 to 95 mass%, and particularly preferably 15 to 90 mass%.

[0095] [Energy ray curable compounds] The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) includes a monomer or oligomer having an energy ray-polymerizable unsaturated group and capable of being cured by irradiation with energy rays. Among the energy ray-curable compounds, examples of the monomer include polyvalent (meth)acrylates such as trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, and 1,6-hexanediol (meth)acrylate; urethane (meth)acrylate; polyester (meth)acrylate; polyether (meth)acrylate; and epoxy (meth)acrylate. Among the energy ray-curable compounds, examples of the oligomer include oligomers obtained by polymerizing the above-mentioned monomers. The energy ray curable compound is preferably a urethane (meth)acrylate or a urethane (meth)acrylate oligomer, since it has a relatively large molecular weight and is less likely to reduce the storage modulus of the pressure-sensitive adhesive layer.

[0096] The pressure-sensitive adhesive composition (I-1) may contain only one type of energy ray-curable compound, or two or more types. When two or more types are contained, the combination and ratio thereof can be selected arbitrarily.

[0097] In the pressure-sensitive adhesive composition (I-1), the content of the energy ray-curable compound relative to the total mass of the pressure-sensitive adhesive composition (I-1) is preferably 1 to 95 mass%, more preferably 5 to 90 mass%, and particularly preferably 10 to 85 mass%. When using an energy ray-curable compound that is liquid at a temperature of 23°C and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer, it is preferable that the content of the energy ray-curable compound in the pressure-sensitive adhesive composition (I-1) satisfies the numerical range separately specified below.

[0098] [Crosslinking agent] When the adhesive resin (I-1a) is an acrylic polymer having, in addition to a structural unit derived from a (meth)acrylic acid alkyl ester, a structural unit derived from a functional group-containing monomer, it is preferable that the adhesive composition (I-1) further contains a crosslinking agent.

[0099] The crosslinking agent, for example, reacts with the functional group to crosslink the adhesive resins (I-1a) together. Examples of the crosslinking agent include isocyanate-based crosslinking agents (crosslinking agents having an isocyanate group) such as tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; epoxy-based crosslinking agents (crosslinking agents having a glycidyl group) such as ethylene glycol glycidyl ether; aziridine-based crosslinking agents (crosslinking agents having an aziridinyl group) such as hexa[1-(2-methyl)-aziridinyl]triphosphatriazine; metal chelate-based crosslinking agents (crosslinking agents having a metal chelate structure) such as aluminum chelate; and isocyanurate-based crosslinking agents (crosslinking agents having an isocyanuric acid skeleton). The crosslinking agent is preferably an isocyanate-based crosslinking agent from the viewpoints of improving the cohesive strength of the pressure-sensitive adhesive and thereby improving the adhesive strength of the pressure-sensitive adhesive layer, and of easy availability.

[0100] The crosslinking agent contained in the pressure-sensitive adhesive composition (I-1) may be one type only, or two or more types. When two or more types are contained, the combination and ratio thereof can be selected arbitrarily.

[0101] When a crosslinking agent is used, the content of the crosslinking agent in the pressure-sensitive adhesive composition (I-1) is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass, per 100 parts by mass of the pressure-sensitive adhesive resin (I-1a). When using a crosslinking agent that is liquid at a temperature of 23°C and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer, it is preferable that the content of the crosslinking agent in the pressure-sensitive adhesive composition (I-1) satisfies the numerical range separately specified below.

[0102] [Photopolymerization initiator] The pressure-sensitive adhesive composition (I-1) may further contain a photopolymerization initiator. The pressure-sensitive adhesive composition (I-1) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

[0103] Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 2,2-dimethoxy-1,2-diphenylethane-1-one; acyl phosphinates such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Examples of such compounds include phosphine oxide compounds; sulfide compounds such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; and 2-chloroanthraquinone. As the photopolymerization initiator, for example, a quinone compound such as 1-chloroanthraquinone; a photosensitizer such as an amine, and the like can also be used.

[0104] The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-1) may be only one type, or may be two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0105] When a photopolymerization initiator is used, the content of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-1) is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the energy ray-curable compound. When using a photopolymerization initiator that is liquid at a temperature of 23°C and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer, it is preferable that the content of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-1) satisfies a numerical range separately defined as described later.

[0106] [Other additives] The pressure-sensitive adhesive composition (I-1) may contain other additives that do not fall into any of the above-mentioned components, as long as the effects of the present invention are not impaired. Examples of the other additives include known additives such as antistatic agents, antioxidants, softeners (plasticizers), fillers, rust inhibitors, colorants (pigments, dyes), sensitizers, tackifiers, reaction retarders, and crosslinking accelerators (catalysts).

[0107] The reaction retarder is, for example, a component for suppressing the progress of unintended crosslinking reaction in the pressure-sensitive adhesive composition (I-1) during storage due to the action of a catalyst mixed in the pressure-sensitive adhesive composition (I-1). For example, the reaction retarder may be one that forms a chelate complex by chelating with the catalyst, and more specifically, one that has two or more carbonyl groups (-C(=O)-) in one molecule.

[0108] The other additives contained in the pressure-sensitive adhesive composition (I-1) may be of only one type, or of two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0109] The content of other additives in the pressure-sensitive adhesive composition (I-1) is not particularly limited and may be appropriately selected depending on the type of additive. When using other additives that are liquid at a temperature of 23°C and do not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer, the content of such additives in the pressure-sensitive adhesive composition (I-1) preferably satisfies a numerical range separately specified below.

[0110] [solvent] The pressure-sensitive adhesive composition (I-1) may contain a solvent. By containing a solvent, the pressure-sensitive adhesive composition (I-1) has improved suitability for application to a surface to be coated.

[0111] The solvent is preferably an organic solvent. Examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; esters (carboxylates) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; aliphatic hydrocarbons such as cyclohexane and n-hexane; aromatic hydrocarbons such as toluene and xylene; and alcohols such as 1-propanol and 2-propanol.

[0112] [Component (γ2)] The component (γ2) in the pressure-sensitive adhesive composition (I-1) is liquid at a temperature of 23° C. Moreover, the component (γ2) does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer (i.e., does not react with the main component). A component that has a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer and is liquid at a temperature of 23° C. does not migrate from the pressure-sensitive adhesive layer to the intermediate layer by reacting with the main component in the pressure-sensitive adhesive layer, and as a result, does not migrate to the film-like adhesive. In the present embodiment, the component (γ2) that does not have the functional group and is liquid at a temperature of 23° C. and is not capable of inhibiting migration from the pressure-sensitive adhesive layer to the film-like adhesive is inhibited from migrating from the pressure-sensitive adhesive layer to the film-like adhesive, instead of the component that has the functional group and is liquid at a temperature of 23° C. For example, when the main component has a hydroxyl group or an amino group, the functional group that reacts with the main component can be an isocyanate group.

[0113] The component (γ2) is not particularly limited as long as it satisfies these conditions, and can be selected arbitrarily according to the purpose. The components contained in the pressure-sensitive adhesive composition (I-1) that do not correspond to either the pressure-sensitive adhesive resin (I-1a) or the solvent, that is, among the energy ray curable compound, the crosslinking agent, the photopolymerization initiator, and other additives, are liquid at a temperature of 23° C. and do not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer, are the component (γ2). The pressure-sensitive adhesive layer does not usually contain a solvent. Preferred examples of the component (γ2) include antistatic agents and tackifiers.

[0114] (Antistatic agent in liquid form at 23°C) The antistatic agent that is liquid at a temperature of 23° C. may be a known one such as a conductive compound, and is not particularly limited. Examples of the antistatic agent include various ionic liquids. Examples of the ionic liquid include known ionic liquids such as pyrimidinium salts, pyridinium salts, piperidinium salts, pyrrolidinium salts, imidazolium salts, morpholinium salts, sulfonium salts, phosphonium salts, and ammonium salts.

[0115] The pressure-sensitive adhesive composition (I-1) may contain only one type of component (γ2), or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0116] When the component (γ2) is used, the content of the component (γ2) in the pressure-sensitive adhesive composition (I-1) and the pressure-sensitive adhesive layer can be appropriately adjusted depending on the type of component (γ2). In the pressure-sensitive adhesive composition (I-1) and the pressure-sensitive adhesive layer, the content of component (γ2) is preferably 0.1 to 40 parts by mass per 100 parts by mass of the pressure-sensitive adhesive resin (I-1a). When the content is equal to or less than the upper limit, migration of component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive is further suppressed. When the content is equal to or more than the lower limit, the effect obtained by using component (γ2) is further enhanced.

[0117] In particular, when component (γ2) is an antistatic agent, the content of component (γ2) (antistatic agent) in the pressure-sensitive adhesive composition (I-1) and the pressure-sensitive adhesive layer is preferably 1 to 7 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the pressure-sensitive adhesive resin (I-1a). When the content is equal to or less than the upper limit, migration of component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive is further suppressed, and excessive use of component (γ2) is suppressed. When the content is equal to or more than the lower limit, the effect obtained by using component (γ2) is enhanced.

[0118] <Adhesive composition (I-2)> As described above, the adhesive composition (I-2) contains an energy ray-curable adhesive resin (I-2a) in which an unsaturated group has been introduced into the side chain of a non-energy ray-curable adhesive resin (I-1a). The pressure-sensitive adhesive composition (I-2) may or may not further contain the component (γ2) in addition to the above. In the pressure-sensitive adhesive composition (I-2), the pressure-sensitive adhesive resin (I-2a) may be the component (γ1), or the pressure-sensitive adhesive resin (I-2a) may be the main component.

[0119] [Adhesive resin (I-2a)] The adhesive resin (I-2a) can be obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group.

[0120] The unsaturated group-containing compound is a compound that, in addition to the energy ray-polymerizable unsaturated group, further has a group that can bond to the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a). Examples of the energy ray-polymerizable unsaturated group include a (meth)acryloyl group, a vinyl group (ethenyl group), and an allyl group (2-propenyl group), and the like, with a (meth)acryloyl group being preferred. Examples of groups capable of bonding to functional groups in the adhesive resin (I-1a) include isocyanate groups and glycidyl groups capable of bonding to hydroxyl groups or amino groups, and hydroxyl groups and amino groups capable of bonding to carboxy groups or epoxy groups.

[0121] Examples of the unsaturated group-containing compound include (meth)acryloyloxyethyl isocyanate, (meth)acryloyl isocyanate, and glycidyl (meth)acrylate.

[0122] The adhesive composition (I-2) may contain only one type of adhesive resin (I-2a), or two or more types of adhesive resins. When two or more types of adhesive resins are contained, the combination and ratio thereof can be selected arbitrarily.

[0123] In the pressure-sensitive adhesive composition (I-2), the content of the adhesive resin (I-2a) relative to the total mass of the pressure-sensitive adhesive composition (I-2) is preferably 5 to 99 mass%, more preferably 10 to 95 mass%, and particularly preferably 10 to 90 mass%.

[0124] [Crosslinking agent] When the adhesive resin (I-2a) is, for example, an acrylic polymer having a structural unit derived from a functional group-containing monomer similar to that in the adhesive resin (I-1a), the adhesive composition (I-2) may further contain a crosslinking agent.

[0125] The crosslinking agent in the pressure-sensitive adhesive composition (I-2) may be the same as the crosslinking agent in the pressure-sensitive adhesive composition (I-1). The crosslinking agent contained in the pressure-sensitive adhesive composition (I-2) may be one type only, or two or more types. When two or more types are contained, the combination and ratio thereof can be selected arbitrarily.

[0126] When a crosslinking agent is used, the content of the crosslinking agent in the pressure-sensitive adhesive composition (I-2) is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass, per 100 parts by mass of the pressure-sensitive adhesive resin (I-2a). When using a crosslinking agent that is liquid at a temperature of 23°C and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer, it is preferable that the content of the crosslinking agent in the pressure-sensitive adhesive composition (I-2) satisfies the numerical range separately specified below.

[0127] [Photopolymerization initiator] The pressure-sensitive adhesive composition (I-2) may further contain a photopolymerization initiator. The pressure-sensitive adhesive composition (I-2) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

[0128] The photopolymerization initiator in the pressure-sensitive adhesive composition (I-2) may be the same as the photopolymerization initiator in the pressure-sensitive adhesive composition (I-1). The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or may be two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0129] When a photopolymerization initiator is used, the content of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-2) is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass, per 100 parts by mass of the pressure-sensitive adhesive resin (I-2a). When using a photopolymerization initiator that is liquid at a temperature of 23°C and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer, it is preferable that the content of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-2) satisfies the numerical range separately specified as described later.

[0130] [Other additives, solvents] The pressure-sensitive adhesive composition (I-2) may contain other additives that do not fall under any of the above-mentioned components, as long as the effects of the present invention are not impaired. The pressure-sensitive adhesive composition (I-2) may contain a solvent for the same purpose as in the pressure-sensitive adhesive composition (I-1). The other additives and solvents in the pressure-sensitive adhesive composition (I-2) include the same as the other additives and solvents in the pressure-sensitive adhesive composition (I-1), respectively. The other additives and the solvent contained in the pressure-sensitive adhesive composition (I-2) may each be of only one type, or of two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily. The contents of other additives and the solvent in the pressure-sensitive adhesive composition (I-2) are not particularly limited and may be appropriately selected depending on the types thereof. When using other additives that are liquid at a temperature of 23°C and do not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer, it is preferable that the content of such additives in the pressure-sensitive adhesive composition (I-2) satisfies the numerical range separately specified below.

[0131] [Component (γ2)] The component (γ2) in the pressure-sensitive adhesive composition (I-2) is liquid at a temperature of 23° C. Furthermore, the component (γ2) does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer (i.e., does not react with the main component). As in the case of the pressure-sensitive adhesive composition (I-1), the use of the pressure-sensitive adhesive composition (I-2) also inhibits migration of the component (γ2) from the pressure-sensitive adhesive layer to the film-like adhesive.

[0132] The component (γ2) is not particularly limited as long as it satisfies these conditions, and can be selected arbitrarily according to the purpose. The components contained in the pressure-sensitive adhesive composition (I-2) that do not correspond to either the pressure-sensitive adhesive resin (I-2a) or the solvent, that is, among the crosslinking agent, the photopolymerization initiator, and other additives, those that are liquid at a temperature of 23° C. and do not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer are the component (γ2). Preferred examples of the component (γ2) in the adhesive composition (I-2) include the same as the preferred component (γ2) in the adhesive composition (I-1) (antistatic agents, tackifiers, etc.).

[0133] The component (γ2) contained in the pressure-sensitive adhesive composition (I-2) may be one type, or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0134] When the component (γ2) is used, the content of the component (γ2) in the pressure-sensitive adhesive composition (I-2) can be appropriately adjusted depending on the type of the component (γ2). In the pressure-sensitive adhesive composition (I-2) and the pressure-sensitive adhesive layer, the content of component (γ2) is preferably 0.1 to 10 parts by mass per 100 parts by mass of the pressure-sensitive adhesive resin (I-2a). When the content is equal to or less than the upper limit, migration of component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive is further suppressed. When the content is equal to or more than the lower limit, the effect obtained by using component (γ2) is further enhanced.

[0135] In particular, when component (γ2) is an antistatic agent, the content of component (γ2) (antistatic agent) in the pressure-sensitive adhesive composition (I-2) and the pressure-sensitive adhesive layer is preferably 1 to 7 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of the pressure-sensitive adhesive resin (I-2a). When the content is equal to or less than the upper limit, migration of component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive is further suppressed, and excessive use of component (γ2) is suppressed. When the content is equal to or more than the lower limit, the effect obtained by using component (γ2) is enhanced.

[0136] <Adhesive composition (I-3)> As described above, the pressure-sensitive adhesive composition (I-3) contains the pressure-sensitive adhesive resin (I-2a) and an energy ray-curable compound.

[0137] The pressure-sensitive adhesive composition (I-3) may or may not further contain the component (γ2) in addition to the above. In the adhesive composition (I-3), the adhesive resin (I-2a) or the energy ray curable compound may be component (γ1), or the adhesive resin (I-2a) or the energy ray curable compound may be the main component.

[0138] [Adhesive resin (I-2a)] The adhesive resin (I-2a) in the adhesive composition (I-3) may be the same as the adhesive resin (I-2a) in the adhesive composition (I-2). The adhesive composition (I-3) may contain only one type of adhesive resin (I-2a), or two or more types. When two or more types are contained, the combination and ratio thereof can be selected arbitrarily.

[0139] In the pressure-sensitive adhesive composition (I-3), the content of the adhesive resin (I-2a) relative to the total mass of the pressure-sensitive adhesive composition (I-3) is preferably 5 to 99 mass%, more preferably 10 to 95 mass%, and particularly preferably 15 to 90 mass%.

[0140] [Energy ray curable compounds] The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) includes monomers and oligomers that have an energy ray-polymerizable unsaturated group and are curable by irradiation with energy rays, and includes the same as the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1). The pressure-sensitive adhesive composition (I-3) may contain only one type of energy ray-curable compound, or two or more types. When two or more types are contained, the combination and ratio thereof can be selected arbitrarily.

[0141] In the pressure-sensitive adhesive composition (I-3) and the pressure-sensitive adhesive layer, the content of the energy ray-curable compound is preferably 0.01 to 300 parts by mass, more preferably 0.03 to 200 parts by mass, and particularly preferably 0.05 to 100 parts by mass, per 100 parts by mass of the pressure-sensitive adhesive resin (I-2a). When using an energy ray-curable compound that is liquid at a temperature of 23°C and does not have a functional group that reacts with the main component contained in the adhesive layer, it is preferable that the content of the energy ray-curable compound in the adhesive composition (I-3) satisfies the numerical range separately specified below.

[0142] [Photopolymerization initiator] The pressure-sensitive adhesive composition (I-3) may further contain a photopolymerization initiator. The pressure-sensitive adhesive composition (I-3) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

[0143] The photopolymerization initiator in the pressure-sensitive adhesive composition (I-3) may be the same as the photopolymerization initiator in the pressure-sensitive adhesive composition (I-1). The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-3) may be only one type, or may be two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0144] When a photopolymerization initiator is used, the content of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-3) is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the total content of the pressure-sensitive adhesive resin (I-2a) and the energy ray-curable compound. When using a photopolymerization initiator that is liquid at a temperature of 23°C and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer, it is preferable that the content of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-3) satisfies the numerical range separately specified below.

[0145] [Other additives, solvents] The pressure-sensitive adhesive composition (I-3) may contain other additives that do not fall into any of the above-mentioned components, as long as the effects of the present invention are not impaired. The pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as in the pressure-sensitive adhesive composition (I-1). The other additives and solvents in the pressure-sensitive adhesive composition (I-3) include the same as the other additives and solvents in the pressure-sensitive adhesive composition (I-1), respectively. The other additives and the solvent contained in the pressure-sensitive adhesive composition (I-3) may each be of only one type, or of two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily. The contents of other additives and the solvent in the pressure-sensitive adhesive composition (I-3) are not particularly limited and may be appropriately selected depending on the types thereof. When using other additives that are liquid at a temperature of 23°C and do not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer, it is preferable that the content of such additives in the pressure-sensitive adhesive composition (I-3) satisfies the numerical range separately specified below.

[0146] [Component (γ2)] The component (γ2) in the pressure-sensitive adhesive composition (I-3) is liquid at a temperature of 23° C. Furthermore, the component (γ2) does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer (i.e., does not react with the main component). As in the case of the pressure-sensitive adhesive composition (I-1), the use of the pressure-sensitive adhesive composition (I-3) also inhibits migration of the component (γ2) from the pressure-sensitive adhesive layer to the film-like adhesive.

[0147] The component (γ2) is not particularly limited as long as it satisfies these conditions, and can be selected arbitrarily according to the purpose. The components contained in the pressure-sensitive adhesive composition (I-3) that do not correspond to either the pressure-sensitive adhesive resin (I-2a) or the solvent, that is, among the energy ray curable compound, the photopolymerization initiator, and other additives, are liquid at a temperature of 23° C. and do not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer, are the components (γ2). Preferred examples of the component (γ2) in the adhesive composition (I-3) include the same as the preferred component (γ2) in the adhesive composition (I-1) (antistatic agents, tackifiers, etc.).

[0148] The pressure-sensitive adhesive composition (I-3) may contain only one type of component (γ2), or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0149] When the component (γ2) is used, the content of the component (γ2) in the pressure-sensitive adhesive composition (I-3) can be appropriately adjusted depending on the type of the component (γ2). In the pressure-sensitive adhesive composition (I-3) and the pressure-sensitive adhesive layer, the content of component (γ2) is preferably 0.1 to 10 parts by mass per 100 parts by mass of the pressure-sensitive adhesive resin (I-2a). When the content is equal to or less than the upper limit, migration of component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive is further suppressed. When the content is equal to or more than the lower limit, the effect obtained by using component (γ2) is further enhanced.

[0150] In particular, when component (γ2) is an antistatic agent, the content of component (γ2) (antistatic agent) in the pressure-sensitive adhesive composition (I-3) and the pressure-sensitive adhesive layer is preferably 1 to 7 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of the pressure-sensitive adhesive resin (I-2a). When the content is equal to or less than the upper limit, migration of component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive is further suppressed, and excessive use of component (γ2) is suppressed. When the content is equal to or more than the lower limit, the effect obtained by using component (γ2) is enhanced.

[0151] <Adhesive compositions other than the adhesive compositions (I-1) to (I-3)> So far, the adhesive composition (I-1), the adhesive composition (I-2) and the adhesive composition (I-3) have been mainly explained, but the components explained as contained therein can be similarly used in general adhesive compositions other than these three types of adhesive compositions (referred to in this specification as "adhesive compositions other than adhesive compositions (I-1) to (I-3)").

[0152] Examples of pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) include energy ray-curable pressure-sensitive adhesive compositions as well as non-energy ray-curable pressure-sensitive adhesive compositions. Examples of the non-energy ray curable adhesive composition include an adhesive composition (I-4) containing a non-energy ray curable adhesive resin (I-1a) such as an acrylic resin, a urethane resin, a rubber-based resin, a silicone resin, an epoxy-based resin, a polyvinyl ether, a polycarbonate, or an ester-based resin, and those containing an acrylic resin are preferred.

[0153] It is preferable that the pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) contain one or more crosslinking agents, and the content thereof can be the same as that of the above-mentioned pressure-sensitive adhesive composition (I-1) etc.

[0154] <Adhesive composition (I-4)> A preferred example of the adhesive composition (I-4) is one that contains the adhesive resin (I-1a) and a crosslinking agent, and may or may not further contain the component (γ2). In the pressure-sensitive adhesive composition (I-4), the pressure-sensitive adhesive resin (I-1a) may be the component (γ1), or the pressure-sensitive adhesive resin (I-1a) may be the main component.

[0155] [Adhesive resin (I-1a)] The adhesive resin (I-1a) in the adhesive composition (I-4) may be the same as the adhesive resin (I-1a) in the adhesive composition (I-1). The adhesive composition (I-4) may contain only one type of adhesive resin (I-1a), or two or more types. When two or more types are contained, the combination and ratio thereof can be selected arbitrarily.

[0156] In the pressure-sensitive adhesive composition (I-4), the content of the adhesive resin (I-1a) relative to the total mass of the pressure-sensitive adhesive composition (I-4) is preferably 5 to 99 mass%, more preferably 10 to 95 mass%, and particularly preferably 15 to 90 mass%.

[0157] [Crosslinking agent] When the adhesive resin (I-1a) is an acrylic polymer having, in addition to a structural unit derived from a (meth)acrylic acid alkyl ester, a structural unit derived from a functional group-containing monomer, it is preferable that the adhesive composition (I-4) further contains a crosslinking agent.

[0158] The crosslinking agent in the pressure-sensitive adhesive composition (I-4) may be the same as the crosslinking agent in the pressure-sensitive adhesive composition (I-1). The crosslinking agent contained in the pressure-sensitive adhesive composition (I-4) may be one type only, or two or more types. When two or more types are contained, the combination and ratio thereof can be selected arbitrarily.

[0159] In the pressure-sensitive adhesive composition (I-4), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 25 parts by mass, and particularly preferably 0.1 to 10 parts by mass, per 100 parts by mass of the pressure-sensitive adhesive resin (I-1a). When using a crosslinking agent that is liquid at a temperature of 23°C and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer, it is preferable that the content of the crosslinking agent in the pressure-sensitive adhesive composition (I-4) satisfies the numerical range separately specified below.

[0160] [Other additives, solvents] The pressure-sensitive adhesive composition (I-4) may contain other additives that do not fall into any of the above-mentioned components, as long as the effects of the present invention are not impaired. The pressure-sensitive adhesive composition (I-4) may contain a solvent for the same purpose as in the pressure-sensitive adhesive composition (I-1). The other additives and solvents in the pressure-sensitive adhesive composition (I-4) include the same as the other additives and solvents in the pressure-sensitive adhesive composition (I-1), respectively. The other additives and the solvent contained in the pressure-sensitive adhesive composition (I-4) may each be of only one type, or of two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily. The contents of other additives and the solvent in the pressure-sensitive adhesive composition (I-4) are not particularly limited and may be appropriately selected depending on the types thereof. When using other additives that are liquid at a temperature of 23°C and do not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer, it is preferable that the content of such additives in the pressure-sensitive adhesive composition (I-4) satisfies the numerical range separately specified below.

[0161] [Component (γ2)] The component (γ2) in the pressure-sensitive adhesive composition (I-4) is liquid at a temperature of 23° C. Furthermore, the component (γ2) does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer (i.e., does not react with the main component). As in the case of the pressure-sensitive adhesive composition (I-1), the use of the pressure-sensitive adhesive composition (I-4) also inhibits migration of the component (γ2) from the pressure-sensitive adhesive layer to the film-like adhesive.

[0162] The component (γ2) is not particularly limited as long as it satisfies these conditions, and can be selected arbitrarily according to the purpose. The components contained in the pressure-sensitive adhesive composition (I-4) that do not correspond to either the pressure-sensitive adhesive resin (I-1a) or the solvent, that is, among the crosslinking agent and other additives, those that are liquid at a temperature of 23° C. and do not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer, are the component (γ2). Preferred examples of the component (γ2) in the pressure-sensitive adhesive composition (I-4) include the same as the preferred component (γ2) in the pressure-sensitive adhesive composition (I-1) (antistatic agents, tackifiers, etc.).

[0163] The pressure-sensitive adhesive composition (I-4) may contain only one type of component (γ2), or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0164] When the component (γ2) is used, the content of the component (γ2) in the pressure-sensitive adhesive composition (I-4) can be appropriately adjusted depending on the type of the component (γ2). In the pressure-sensitive adhesive composition (I-4) and the pressure-sensitive adhesive layer, the content of component (γ2) is preferably 0.1 to 10 parts by mass per 100 parts by mass of the pressure-sensitive adhesive resin (I-1a). When the content is equal to or less than the upper limit, migration of component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive is further suppressed. When the content is equal to or more than the lower limit, the effect obtained by using component (γ2) is further enhanced.

[0165] In particular, when component (γ2) is an antistatic agent, the content of component (γ2) (antistatic agent) in the pressure-sensitive adhesive composition (I-4) and the pressure-sensitive adhesive layer is preferably 1 to 7 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of the pressure-sensitive adhesive resin (I-1a). When the content is equal to or less than the upper limit, migration of component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive is further suppressed, and excessive use of component (γ2) is suppressed. When the content is equal to or more than the lower limit, the effect obtained by using component (γ2) is enhanced.

[0166] When component (γ2) is used, regardless of whether the pressure-sensitive adhesive composition is any of pressure-sensitive adhesive compositions (I-1) to (I-4), the content of component (γ2) in the pressure-sensitive adhesive layer is preferably 0.1 to 10 parts by mass per 100 parts by mass of the pressure-sensitive adhesive content. In particular, when component (γ2) is an antistatic agent, the content of component (γ2) (antistatic agent) in the adhesive layer is preferably 1 to 7 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of the adhesive content.

[0167] <<Method of manufacturing pressure-sensitive adhesive composition>> The pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3), such as the pressure-sensitive adhesive compositions (I-4), can be obtained by blending the pressure-sensitive adhesive and, as necessary, components other than the pressure-sensitive adhesive, for example, components for constituting the pressure-sensitive adhesive composition. The order of addition of the components when blending is not particularly limited, and two or more components may be added simultaneously. When a solvent is used, the solvent may be used by mixing it with any of the other ingredients to pre-dilute the ingredients, or the solvent may be used by mixing it with any of the other ingredients without pre-diluting the ingredients. The method for mixing the components during blending is not particularly limited, and may be appropriately selected from known methods such as a method of mixing by rotating a stirrer or stirring blades, a method of mixing using a mixer, a method of mixing by adding ultrasound, etc. The temperature and time during addition and mixing of each component are not particularly limited as long as the components do not deteriorate, and may be adjusted appropriately. A temperature of 15 to 30°C is preferred.

[0168] ○Intermediate layer, intermediate layer forming composition The intermediate layer is in the form of a sheet or film, and contains the non-silicon resin (β1) as a main component. The intermediate layer may contain only the non-silicon-based resin (β1) (consisting of the non-silicon-based resin (β1)), or may contain the non-silicon-based resin (β1) and other components.

[0169] The intermediate layer can be formed, for example, by using a composition for forming an intermediate layer containing the non-silicon resin (β1). For example, the intermediate layer can be formed at a desired location by applying the composition for forming an intermediate layer to a surface on which the intermediate layer is to be formed and drying it as necessary.

[0170] In the intermediate layer, the ratio of the total content of one or more components contained in the intermediate layer, which will be described later, to the total mass of the intermediate layer does not exceed 100 mass %. Similarly, in the composition for forming an intermediate layer, the ratio of the total content of one or more components contained in the composition for forming an intermediate layer, which will be described later, to the total mass of the composition for forming an intermediate layer does not exceed 100 mass %.

[0171] The intermediate layer forming composition can be applied in the same manner as in the application of the pressure-sensitive adhesive composition described above.

[0172] The drying conditions of the composition for forming an intermediate layer are not particularly limited. When the composition for forming an intermediate layer contains a solvent described later, it is preferable to heat-dry it, and in this case, it is preferable to dry it under conditions of, for example, 60 to 130° C. for 1 to 6 minutes.

[0173] The non-silicon resin (β1) has a weight average molecular weight of 20,000 to 100,000. In order to further improve the suitability of the sheet for manufacturing semiconductor device for dividing the above-mentioned semiconductor wafers, the weight average molecular weight of the non-silicon based resin (β1) may be, for example, any one of 20,000 to 80,000, 20,000 to 60,000, and 20,000 to 40,000.

[0174] The component having the greatest content (parts by mass) in the intermediate layer is the non-silicon resin (β1). In order to achieve a greater effect by the intermediate layer containing the non-silicon-based resin (β1), the ratio of the content of the non-silicon-based resin (β1) to the total mass of the intermediate layer (in other words, the ratio of the content of the non-silicon-based resin (β1) to the total content of all components other than the solvent in the composition for forming the intermediate layer) is preferably 75 mass% or more, more preferably 85 mass% or more, and may be, for example, any one of 95 mass% or more, 97 mass% or more, and 99 mass% or more. On the other hand, the proportion is 100% by mass or less.

[0175] The non-silicon-based resin (β1) is not particularly limited as long as it is a resin component that does not contain silicon atoms as constituent atoms and has a weight average molecular weight of 20,000 to 100,000. The non-silicon resin (β1) may be, for example, either a polar resin having a polar group, or a non-polar resin having no polar group. For example, the non-silicon-based resin (β1) is preferably a polar resin in that it has high solubility in the intermediate layer forming composition and the intermediate layer forming composition has higher coatability.

[0176] The non-silicon resin (β1) may be, for example, a homopolymer that is a polymer of one type of monomer (in other words, having only one type of structural unit), or a copolymer that is a polymer of two or more types of monomers (in other words, having two or more types of structural units).

[0177] Examples of the polar group include a carbonyloxy group (-C(=O)-O-), an oxycarbonyl group (-OC(=O)-), and the like.

[0178] The polar resin may have only a constituent unit having a polar group, or may have both a constituent unit having a polar group and a constituent unit not having a polar group.

[0179] Examples of the structural unit having a polar group include a structural unit derived from vinyl acetate. Examples of the structural unit not having a polar group include a structural unit derived from ethylene.

[0180] In the polar resin, the ratio of the mass of the structural unit having a polar group to the total mass of all structural units is preferably 45% by mass or less, more preferably 30% by mass or less. The lower the ratio, the higher the effect of suppressing the migration of component (α2) in the film-like adhesive to the pressure-sensitive adhesive layer and the migration of component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive. On the other hand, the ratio is preferably 5% by mass or more, more preferably 7.5% by mass or more, and even more preferably 10% by mass or more. The higher the ratio, the more significantly the polar resin exhibits the characteristic of having a polar group.

[0181] In the polar resin, the mass ratio of the structural unit having a polar group to the total mass of all structural units can be appropriately adjusted within a range set by any combination of any of the upper limit values ​​and any of the lower limit values ​​described above. For example, in one embodiment, the ratio may be any of 5 to 45 mass%, 7.5 to 45 mass%, 10 to 45 mass%, 5 to 30 mass%, 7.5 to 30 mass%, and 10 to 30 mass%.

[0182] The polar resin may, for example, be an ethylene-vinyl acetate copolymer. Among them, the preferred polar resin is, for example, an ethylene-vinyl acetate copolymer in which the mass ratio of the structural unit derived from vinyl acetate to the total mass of all structural units (sometimes referred to as the "content of structural units derived from vinyl acetate" in this specification) is within any of the numerical ranges of the above-mentioned "mass ratio of structural units having polar groups", and is particularly preferably 30% by mass or less. That is, a particularly preferred polar resin is, for example, an ethylene-vinyl acetate copolymer in which the mass ratio of the structural unit derived from vinyl acetate to the total mass of all structural units is 30% by mass or less. In other words, a particularly preferred polar resin is, for example, an ethylene-vinyl acetate copolymer in which the mass ratio of the structural unit derived from ethylene to the total mass of all structural units is 70% by mass or more.

[0183] Examples of the non-polar resin include polyethylene (PE) such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), metallocene-catalyzed linear low-density polyethylene (metallocene LLDPE), medium-density polyethylene (MDPE), and high-density polyethylene (HDPE); and polyolefins such as polypropylene (PP).

[0184] The non-silicon-based resin (β1) contained in the composition for forming an intermediate layer and the intermediate layer may be one type or two or more types, and when there are two or more types, the combination and ratio thereof can be selected arbitrarily. For example, the composition for forming an intermediate layer and the intermediate layer may contain one or more types of non-silicon-based resins (β1) that are polar resins, and may not contain any non-silicon-based resins (β1) that are non-polar resins, or may contain one or more types of non-silicon-based resins (β1) that are non-polar resins, and may not contain any non-silicon-based resins (β1) that are polar resins, or may contain one or more types of both a non-silicon-based resin (β1) that is a polar resin and a non-silicon-based resin (β1) that is a non-polar resin. The intermediate layer forming composition and the intermediate layer preferably contain at least the non-silicon based resin (β1), which is a polar resin.

[0185] The intermediate layer forming composition and the intermediate layer preferably contain one or more selected from the group consisting of ethylene vinyl acetate copolymer and polyolefin as the non-silicon-based resin (β1). In the semiconductor device manufacturing sheet having such an intermediate layer, when the film-like adhesive contains the component (α2), the migration of the component (α2) in the film-like adhesive to the pressure-sensitive adhesive layer is further suppressed, and when the pressure-sensitive adhesive layer contains the component (γ2), the migration of the component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive is further suppressed.

[0186] In the intermediate layer forming composition and the intermediate layer, the content of the non-silicon-based resin (β1), which is a polar resin, relative to the total content of the non-silicon-based resin (β1) is preferably 80% by mass or more, more preferably 90% by mass or more, and may be, for example, any one of 95% by mass or more, 97% by mass or more, and 99% by mass or more. When the content is equal to or more than the lower limit, the effect of using the polar resin is more significantly obtained. On the other hand, the proportion is 100% by mass or less.

[0187] That is, in the composition for forming an intermediate layer and the intermediate layer, the ratio of the content of the non-silicon-based resin (β1), which is a non-polar resin, to the total content of the non-silicon-based resin (β1) is preferably 20 mass% or less, more preferably 10 mass% or less, and may be, for example, any one of 5 mass% or less, 3 mass% or less, and 1 mass% or less. On the other hand, the ratio is 0% by mass or more.

[0188] In terms of ease of handling, the composition for forming the intermediate layer preferably contains a solvent in addition to the non-silicon-based resin (β1), and may contain a component (sometimes referred to as an "additive" in this specification) that does not fall into either the non-silicon-based resin (β1) or the solvent. The intermediate layer may contain only the non-silicon based resin (β1), or may contain both the non-silicon based resin (β1) and the additive.

[0189] The additives may be either resin components (sometimes referred to as "other resin components" in this specification) or non-resin components.

[0190] Examples of the other resin components include non-silicon-based resins having a weight average molecular weight (Mw) of more than 100,000 (Mw>100,000) and silicon-based resins.

[0191] There are no particular limitations on the non-silicon-based resin having a weight average molecular weight of more than 100,000, so long as it satisfies these conditions.

[0192] The intermediate layer containing the silicon-based resin makes it easier to pick up the semiconductor chip with the film-like adhesive attached thereto, as described below.

[0193] The silicon-based resin is not particularly limited as long as it is a resin component having silicon atoms as constituent atoms. For example, the weight average molecular weight of the silicon-based resin is not particularly limited.

[0194] Preferred silicon-based resins include, for example, resin components that exhibit a releasing effect against pressure-sensitive adhesive components, and siloxane-based resins (resin components having a siloxane bond (-Si-O-Si-), also known as siloxane-based compounds) are more preferred.

[0195] The siloxane-based resin may, for example, be polydialkylsiloxane. The alkyl group in the polydialkylsiloxane preferably has 1 to 20 carbon atoms. The polydialkylsiloxane may, for example, be polydimethylsiloxane.

[0196] The non-resin component is not particularly limited and may be, for example, either an organic compound or an inorganic compound.

[0197] The additives contained in the intermediate layer-forming composition and the intermediate layer may be of only one type, or may be of two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily. For example, the composition for forming an intermediate layer and the intermediate layer may contain, as the additives, one or more resin components and no non-resin components, may contain one or more non-resin components and no resin components, or may contain one or more resin components and one or more non-resin components.

[0198] When the intermediate layer forming composition and the intermediate layer contain the additives, the ratio of the content of the non-silicon-based resin (β1) in the intermediate layer to the total mass of the intermediate layer (in other words, the ratio of the content of the non-silicon-based resin (β1) to the total content of all components other than the solvent in the intermediate layer forming composition) is preferably 90 to 99.99 mass%, and may be, for example, any of 90 to 97.5 mass%, 90 to 95 mass%, and 90 to 92.5 mass%, or any of 92.5 to 99.99 mass%, 95 to 99.99 mass%, and 97.5 to 99.99 mass%, or may be 92.5 to 97.5 mass%. When the intermediate layer forming composition and the intermediate layer contain the additives, the ratio of the content of the additives in the intermediate layer to the total mass of the intermediate layer (in other words, the ratio of the content of the additives to the total content of all components other than the solvent in the intermediate layer forming composition) is preferably 0.01 to 10 mass%, and may be, for example, any of 2.5 to 10 mass%, 5 to 10 mass%, and 7.5 to 10 mass%, or any of 0.01 to 7.5 mass%, 0.01 to 5 mass%, and 0.01 to 2.5 mass%, or may be 2.5 to 7.5 mass%.

[0199] The solvent contained in the composition for forming an intermediate layer is not particularly limited, but preferred examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone. The intermediate layer forming composition may contain only one type of solvent, or two or more types. When two or more types are contained, the combination and ratio thereof can be selected arbitrarily.

[0200] The solvent contained in the composition for forming an intermediate layer is preferably tetrahydrofuran or the like, since the components contained in the composition for forming an intermediate layer can be mixed more uniformly.

[0201] The content of the solvent in the composition for forming an intermediate layer is not particularly limited, and may be appropriately selected depending on, for example, the types of components other than the solvent.

[0202] As described below, from the viewpoint of making it easier to pick up the semiconductor chip with the film-like adhesive, a preferred intermediate layer is, for example, one that contains an ethylene-vinyl acetate copolymer, which is the non-silicon-based resin (β1), and a siloxane-based compound, which is the additive, in which the ratio of the content of the ethylene-vinyl acetate copolymer (the non-silicon-based resin (β1)) to the total mass of the intermediate layer is within any of the numerical ranges described above, and the ratio of the content of the siloxane-based compound (the additive) to the total mass of the intermediate layer is within any of the numerical ranges described above. For example, such an intermediate layer may contain an ethylene-vinyl acetate copolymer, which is the non-silicon resin (β1), and a siloxane compound, which is the additive, and the content of the ethylene-vinyl acetate copolymer in the intermediate layer relative to the total mass of the intermediate layer is 90 to 99.99% by mass, and the content of the siloxane compound in the intermediate layer relative to the total mass of the intermediate layer is 0.01 to 10% by mass. However, this is one example of a preferred intermediate layer.

[0203] A more preferred intermediate layer is, for example, one in which the intermediate layer contains the non-silicon resin (β1) ethylene-vinyl acetate copolymer and the additive siloxane compound, in which the ratio of the mass of the structural units derived from vinyl acetate to the total mass of all structural units in the ethylene-vinyl acetate copolymer (in other words, the content of the structural units derived from vinyl acetate) is 30 mass% or less, the ratio of the content of the ethylene-vinyl acetate copolymer to the total mass of the intermediate layer in the intermediate layer is 90 to 99.99 mass%, and the ratio of the content of the siloxane compound to the total mass of the intermediate layer in the intermediate layer is 0.01 to 10 mass%. However, this is one example of a more preferred intermediate layer.

[0204] When the surface of the intermediate layer on the film-like adhesive side of the sheet for manufacturing semiconductor device (for example, first surface 13a of intermediate layer 13 in FIG. 1) is analyzed by X-ray photoelectron spectroscopy (sometimes referred to as "XPS" in this specification), the ratio of the silicon concentration to the total concentration of carbon, oxygen, nitrogen and silicon (sometimes abbreviated as "silicon concentration ratio" in this specification) is preferably 1 to 20% on a molar basis of the element. By using a sheet for manufacturing semiconductor device having such an intermediate layer, it is possible to more easily pick up a semiconductor chip with a film-like adhesive, as described below.

[0205] XPS analysis can be performed by using an X-ray photoelectron spectrometer with the film-like adhesive side of the intermediate layer as the analysis subject, setting the X-ray irradiation angle to 45°, the X-ray beam diameter to 20 μmφ, and the output to 4.5 W.

[0206] The silicon concentration ratio is calculated by the following formula: [Measured silicon concentration (atomic %) in XPS analysis] / {[Measured carbon concentration (atomic %) in XPS analysis]+[Measured oxygen concentration (atomic %) in XPS analysis]+[Measured nitrogen concentration (atomic %) in XPS analysis]+[Measured silicon concentration (atomic %) in XPS analysis]}×100 It can be calculated as follows.

[0207] In order to make such effects more pronounced, the silicon concentration may be, for example, any one of 4 to 20%, 8 to 20%, and 12 to 20%, or any one of 1 to 16%, 1 to 12%, and 1 to 8%, or any one of 4 to 16% and 8 to 12%, on a molar basis of the element.

[0208] When the XPS analysis is performed as described above, there is a possibility that other elements not corresponding to any of carbon, oxygen, nitrogen, and silicon are detected on the surface (the surface to be analyzed by XPS) of the intermediate layer. However, even if the other elements are detected, their concentrations are usually very small, so that the silicon concentration ratio can be calculated with high accuracy by using the measured values ​​of the concentrations of carbon, oxygen, nitrogen, and silicon.

[0209] The intermediate layer may consist of one layer (single layer) or may consist of two or more layers. If it consists of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

[0210] As explained above, the first test piece made of the non-silicon based resin (β1) contained in the intermediate layer satisfies the relationship between the formulas (X1) and (X2).

[0211] As explained above, the maximum width of the intermediate layer is preferably smaller than the maximum width of the pressure-sensitive adhesive layer and the maximum width of the substrate. The maximum width of the intermediate layer can be appropriately selected in consideration of the size of the semiconductor wafer. For example, the maximum width of the intermediate layer may be 150 to 160 mm, 200 to 210 mm, or 300 to 310 mm. These three numerical ranges correspond to a semiconductor wafer having a maximum width in a direction parallel to the attachment surface with the semiconductor device manufacturing sheet of 150 mm, 200 mm, or 300 mm. However, as explained above, when the semiconductor device manufacturing sheet (film-like adhesive) is expanded after dicing involving the formation of a modified layer in the semiconductor wafer, the semiconductor device manufacturing sheet is attached to the semiconductor chips as described below by grouping a large number of semiconductor chips (semiconductor chip group) after dicing.

[0212] In this specification, unless otherwise specified, the "width of the intermediate layer" means, for example, the "width of the intermediate layer in a direction parallel to the first surface of the intermediate layer." For example, in the case of an intermediate layer having a circular planar shape, the maximum value of the width of the intermediate layer described above is the diameter of the circle that is the planar shape. This also applies to semiconductor wafers. That is, the "width of the semiconductor wafer" means the "width of the semiconductor wafer in a direction parallel to the surface of the semiconductor wafer attached to the sheet for manufacturing semiconductor device." For example, in the case of a semiconductor wafer having a circular planar shape, the maximum value of the width of the semiconductor wafer is the diameter of the circle that is the planar shape.

[0213] The maximum width of the intermediate layer of 150 to 160 mm means that it is equal to or larger than the maximum width of the semiconductor wafer of 150 mm by not exceeding 10 mm. Similarly, the maximum width of the intermediate layer of 200 to 210 mm means that it is equal to or larger than the maximum width of the semiconductor wafer of 200 mm by not exceeding 10 mm. Similarly, the maximum width of the intermediate layer of 300 to 310 mm means that it is equal to or larger than the maximum width of the semiconductor wafer of 300 mm by not exceeding 10 mm. That is, in this embodiment, the difference between the maximum width of the intermediate layer and the maximum width of the semiconductor wafer may be, for example, 0 to 10 mm, regardless of whether the maximum width of the semiconductor wafer is 150 mm, 200 mm, or 300 mm.

[0214] The thickness of the intermediate layer can be appropriately selected depending on the purpose, but is preferably 5 to 150 μm, more preferably 5 to 120 μm, and may be, for example, any of 10 to 90 μm and 10 to 60 μm, or any of 30 to 120 μm and 60 to 120 μm. When the thickness of the intermediate layer is equal to or greater than the lower limit, the structure of the intermediate layer is more stable. When the thickness of the intermediate layer is equal to or less than the upper limit, the film-like adhesive can be cut more easily during blade dicing and the expansion of the sheet for manufacturing semiconductor device (film-like adhesive). Here, "the thickness of the intermediate layer" means the thickness of the entire intermediate layer. For example, the thickness of an intermediate layer consisting of multiple layers means the total thickness of all layers that make up the intermediate layer.

[0215] When the intermediate layer contains the silicon-based resin, particularly when the compatibility between the silicon-based resin and the non-silicon-based resin (β1) that is the main component is low, the silicon-based resin in the intermediate layer in the sheet for manufacturing semiconductor device is likely to be unevenly distributed on both sides (the first side and the opposite side) of the intermediate layer and the areas nearby. The stronger this tendency is, the easier it is for the film-like adhesive adjacent to (in direct contact with) the intermediate layer to peel off from the intermediate layer, and as described below, the easier it is to pick up the semiconductor chip with the film-like adhesive. For example, when comparing intermediate layers that are different from each other only in thickness and are the same in other respects such as composition and the area of ​​both sides, the ratio (mass %) of the content of the silicon-based resin to the total mass of the intermediate layers is the same for these intermediate layers. However, the content (mass parts) of the silicon-based resin in the intermediate layer is greater in the thick intermediate layer than in the thin intermediate layer. Therefore, when the silicon-based resin is likely to be unevenly distributed in the intermediate layer as described above, the thick intermediate layer will have a greater amount of silicon-based resin unevenly distributed on both sides (the first surface and the surface opposite thereto) and the adjacent areas than the thin intermediate layer. Therefore, even without changing the ratio, it is possible to adjust the pick-up suitability of the semiconductor chip with the film-like adhesive by adjusting the thickness of the intermediate layer in the semiconductor device manufacturing sheet. For example, by increasing the thickness of the intermediate layer in the semiconductor device manufacturing sheet, the semiconductor chip with the film-like adhesive can be picked up more easily.

[0216] The intermediate layer forming composition can be obtained by blending the respective components constituting the intermediate layer. The composition for forming the intermediate layer can be produced, for example, by the same method as that for the pressure-sensitive adhesive composition described above, except that the types of blended components are different.

[0217] ○Film adhesive The film-like adhesive has a curing property, preferably a thermosetting property, and preferably a pressure-sensitive adhesive property. A film-like adhesive having both a thermosetting property and a pressure-sensitive adhesive property can be applied to various adherends by lightly pressing it against the adherend in an uncured state. The film-like adhesive may also be one that can be applied to various adherends by heating and softening it. The film-like adhesive finally becomes a cured product with high impact resistance by curing, and this cured product can retain sufficient adhesive properties even under harsh conditions of high temperature and high humidity.

[0218] A preferred film adhesive is, for example, one that contains a polymer component (a) and a thermosetting component (b).

[0219] The film-like adhesive may or may not contain the component (α2). The component (α2) is a component other than the polymer component (a), and may be the thermosetting component (b) or a component other than the thermosetting component (b).

[0220] The film-like adhesive may or may not contain a component (α1) that is solid at a temperature of 23° C. as the polymer component (a). The film-like adhesive may or may not contain a polymer component (a) as the main component. The film-like adhesive may or may not contain the component (α1) as the main component. When the component (α1) is the main component, the weight average molecular weight of the component (α1) is 20,000 or more, and the component with the largest content (parts by mass) in the film-like adhesive is the component (α1).

[0221] The film-like adhesive preferably contains the component (α1), and may contain both component (α1) and component (α2), or may contain component (α1) but not component (α2).

[0222] When the film-like adhesive contains component (α1) as the main component, component (α1) is preferably an acrylic resin having a structural unit derived from a (meth)acrylic acid ester.

[0223] The film-like adhesive can be formed using an adhesive composition containing the constituent materials thereof. For example, the adhesive composition can be applied to a surface on which the film-like adhesive is to be formed, and then dried as necessary to form the film-like adhesive at the desired site. The ratio of the contents of the components that do not vaporize at room temperature in the adhesive composition is usually the same as the ratio of the contents of the components in the film-like adhesive.

[0224] In the film-like adhesive, the proportion of the total content of one or more components contained in the film-like adhesive, which will be described later, relative to the total mass of the film-like adhesive does not exceed 100 mass %. Similarly, in the adhesive composition, the proportion of the total content of one or more components contained in the adhesive composition, which will be described later, relative to the total mass of the adhesive composition does not exceed 100 mass %.

[0225] The adhesive composition can be applied in the same manner as in the application of the pressure-sensitive adhesive composition described above.

[0226] The drying conditions for the adhesive composition are not particularly limited. When the adhesive composition contains a solvent described below, it is preferable to heat-dry it, and in this case, it is preferable to dry it under conditions of, for example, 70 to 130° C. for 10 seconds to 5 minutes.

[0227] The film-like adhesive may consist of one layer (single layer) or may consist of two or more layers. If it consists of multiple layers, these multiple layers may be the same or different, and the combination of these multiple layers is not particularly limited.

[0228] When the sheet for manufacturing semiconductor device is viewed from above in a plan view, the area of ​​the film-like adhesive (i.e., the area of ​​the first surface) is preferably set smaller than the area of ​​the base material (i.e., the area of ​​the first surface) and the area of ​​the adhesive layer (i.e., the area of ​​the first surface) so as to be close to the area of ​​the semiconductor wafer before division. In such a sheet for manufacturing semiconductor device, a part of the first surface of the adhesive layer has an area (i.e., the non-laminated area) that is not in contact with the intermediate layer and the film-like adhesive. This makes it easier to expand the sheet for manufacturing semiconductor device (film-like adhesive), and since the force applied to the film-like adhesive during expansion is not dispersed, the film-like adhesive can be cut more easily.

[0229] As explained above, the maximum width of the film-like adhesive is preferably smaller than the maximum width of the pressure-sensitive adhesive layer and the maximum width of the substrate. The maximum width of the film adhesive may be the same as the maximum width of the intermediate layer described above with respect to the size of the semiconductor wafer. That is, the maximum width of the film-like adhesive can be appropriately selected in consideration of the size of the semiconductor wafer. For example, the maximum width of the film-like adhesive may be 150 to 160 mm, 200 to 210 mm, or 300 to 310 mm. These three numerical ranges correspond to a semiconductor wafer having a maximum width in a direction parallel to the attachment surface with the semiconductor device manufacturing sheet of 150 mm, 200 mm, or 300 mm.

[0230] In this specification, unless otherwise specified, the "width of the film-like adhesive" means, for example, "the width of the film-like adhesive in a direction parallel to the first surface of the film-like adhesive." For example, in the case of a film-like adhesive having a circular planar shape, the maximum value of the width of the film-like adhesive described above is the diameter of the circle that is the planar shape. Furthermore, unless otherwise specified, the "width of the film-like adhesive" does not mean the width of the film-like adhesive after cutting during the manufacturing process of semiconductor chips with film-like adhesive described below, but rather the "width of the film-like adhesive before cutting (uncut)."

[0231] The maximum width of the film-like adhesive of 150 to 160 mm means that it is equal to or larger than the maximum width of a semiconductor wafer of 150 mm by not exceeding 10 mm. Similarly, the maximum width of the film-like adhesive of 200 to 210 mm means that it is equal to or larger than the maximum width of a semiconductor wafer of 200 mm by not exceeding 10 mm. Similarly, the maximum width of the film-like adhesive of 300 to 310 mm means that it is equal to or larger than the maximum width of a semiconductor wafer of 300 mm by not exceeding 10 mm. That is, in this embodiment, the difference between the maximum width of the film-like adhesive and the maximum width of the semiconductor wafer may be, for example, 0 to 10 mm, regardless of whether the maximum width of the semiconductor wafer is 150 mm, 200 mm, or 300 mm.

[0232] In this embodiment, the maximum width of the intermediate layer and the maximum width of the film-like adhesive may both be within any of the above-mentioned numerical ranges. That is, an example of the sheet for manufacturing a semiconductor device of this embodiment is one in which the maximum width of the intermediate layer and the maximum width of the film-like adhesive are both 150 to 160 mm, 200 to 210 mm, or 300 to 310 mm.

[0233] The thickness of the film-like adhesive is not particularly limited, but is preferably 1 to 30 μm, more preferably 2 to 20 μm, and particularly preferably 3 to 10 μm. When the thickness of the film-like adhesive is equal to or greater than the lower limit, a higher adhesive strength to the adherend (semiconductor chip) can be obtained. When the thickness of the film-like adhesive is equal to or less than the upper limit, the film-like adhesive can be cut more easily during blade dicing and the expansion of the semiconductor device manufacturing sheet (film-like adhesive). Here, "thickness of the film-like adhesive" means the thickness of the entire film-like adhesive; for example, the thickness of a film-like adhesive consisting of multiple layers means the total thickness of all layers that make up the film-like adhesive. Next, the adhesive composition will be described.

[0234] <<Adhesive composition>> A preferred adhesive composition includes, for example, one that contains a polymer component (a) and a thermosetting component (b). In addition to these, the adhesive composition may or may not further contain the component (α2). In the adhesive composition, the polymer component (a) may be the component (α1), or the polymer component (a) may be the main component.

[0235] Each component of the adhesive composition and the film-like adhesive will be described below. The adhesive composition shown below is a preferred example, and the adhesive composition in this embodiment is not limited to the one shown below.

[0236] [Polymer component (a)] The polymer component (a) is a component that can be considered to be formed by a polymerization reaction of a polymerizable compound, and is a polymer compound that imparts film-forming properties, flexibility, etc. to the film-like adhesive and improves adhesion (in other words, stickability) to an adhesion target such as a semiconductor chip. The polymer component (a) has thermoplasticity and does not have thermosetting properties. In this specification, the polymer compound also includes the product of a polycondensation reaction.

[0237] The adhesive composition and film-like adhesive may contain only one type of polymer component (a), or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0238] Examples of the polymer component (a) include acrylic resins, urethane resins, phenoxy resins, silicone resins, and saturated polyester resins. Of these, the polymer component (a) is preferably an acrylic resin.

[0239] In the adhesive composition, the proportion of the content of polymer component (a) relative to the total content of all components other than the solvent (i.e., the proportion of the content of polymer component (a) in the film adhesive relative to the total mass of the film adhesive) is preferably 20 to 75 mass%, more preferably 30 to 65 mass%.

[0240] [Thermosetting component (b)] The thermosetting component (b) has thermosetting properties and is a component for thermally curing the film-like adhesive. The thermosetting component (b) contained in the adhesive composition and film-like adhesive may be one type or two or more types, and when there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0241] Examples of the thermosetting component (b) include epoxy-based thermosetting resins, polyimide resins, and unsaturated polyester resins. Among these, the thermosetting component (b) is preferably an epoxy-based thermosetting resin.

[0242] 〇Epoxy thermosetting resin The epoxy thermosetting resin is composed of an epoxy resin (b1) and a thermosetting agent (b2). The adhesive composition and the film-like adhesive may contain only one type of epoxy thermosetting resin, or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0243] Epoxy resin (b1) The epoxy resin (b1) may be any known substance, such as a polyfunctional epoxy resin, a biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated product, orthocresol novolac epoxy resin, a dicyclopentadiene type epoxy resin, a biphenyl type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a phenylene skeleton type epoxy resin.

[0244] As the epoxy resin (b1), an epoxy resin having an unsaturated hydrocarbon group may be used. The epoxy resin having an unsaturated hydrocarbon group has a higher compatibility with the acrylic resin than the epoxy resin not having an unsaturated hydrocarbon group. Therefore, by using the epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained by using the film-like adhesive is improved.

[0245] The epoxy resin (b1) contained in the adhesive composition and the film-like adhesive may be one type, or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0246] ·Heat hardener (b2) The thermosetting agent (b2) functions as a curing agent for the epoxy resin (b1). The thermosetting agent (b2) may be, for example, a compound having two or more functional groups capable of reacting with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and an anhydride group of an acid group, and the like. The phenolic hydroxyl group, the amino group, or an anhydride group of an acid group is preferable, and the phenolic hydroxyl group or the amino group is more preferable.

[0247] Among the heat curing agents (b2), examples of phenolic curing agents having a phenolic hydroxyl group include polyfunctional phenolic resins, biphenols, novolac-type phenolic resins, dicyclopentadiene-type phenolic resins, and aralkyl-type phenolic resins. Among the heat curing agents (b2), examples of amine-based curing agents having an amino group include dicyandiamide (DICY) and the like.

[0248] The heat curing agent (b2) may have an unsaturated hydrocarbon group.

[0249] The adhesive composition and film-like adhesive may contain only one type of thermosetting agent (b2), or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0250] In the adhesive composition and the film-like adhesive, the content of the thermosetting agent (b2) is preferably 0.1 to 500 parts by mass, more preferably 1 to 200 parts by mass, and may be, for example, any one of 1 to 100 parts by mass, 1 to 50 parts by mass, and 1 to 25 parts by mass, relative to 100 parts by mass of the epoxy resin (b1). When the content of the thermosetting agent (b2) is equal to or greater than the lower limit, the curing of the film-like adhesive proceeds more easily. When the content of the thermosetting agent (b2) is equal to or less than the upper limit, the moisture absorption rate of the film-like adhesive is reduced, and the reliability of the package obtained using the film-like adhesive is further improved.

[0251] In the adhesive composition and film-like adhesive, the content of the thermosetting component (b) (e.g., the total content of the epoxy resin (b1) and the thermosetting agent (b2)) is preferably 5 to 100 parts by mass, more preferably 5 to 75 parts by mass, and particularly preferably 5 to 50 parts by mass, per 100 parts by mass of the polymer component (a), and may be, for example, any of 5 to 35 parts by mass and 5 to 20 parts by mass. When the content of the thermosetting component (b) is within such a range, the peel force between the intermediate layer and the film-like adhesive becomes more stable.

[0252] When using a thermosetting component (b) (e.g., either or both of the epoxy resin (b1) and the thermosetting agent (b2)) that is liquid at a temperature of 23°C and does not have a functional group that reacts with the main component contained in the film-like adhesive, it is preferable that the content of the component in the adhesive composition and the film-like adhesive satisfies the numerical range separately specified below.

[0253] In order to improve various physical properties of the film-like adhesive, the adhesive composition and the film-like adhesive may contain, in addition to the polymer component (a) and the thermosetting component (b), other components not falling under these categories, as necessary. Preferred examples of other components contained in the adhesive composition and the film-like adhesive include a curing accelerator (c), a filler (d), a coupling agent (e), a crosslinking agent (f), an energy ray-curable resin (g), a photopolymerization initiator (h), and a general-purpose additive (i).

[0254] [Cure accelerator (c)] The curing accelerator (c) is a component for adjusting the curing speed of the adhesive composition. Preferred examples of the curing accelerator (c) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; imidazoles (imidazoles in which one or more hydrogen atoms are substituted with groups other than hydrogen atoms) such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole; organic phosphines (phosphines in which one or more hydrogen atoms are substituted with organic groups) such as tributylphosphine, diphenylphosphine, and triphenylphosphine; and tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate.

[0255] The adhesive composition and film-like adhesive may contain only one type of curing accelerator (c), or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0256] When the curing accelerator (c) is used, the content of the curing accelerator (c) in the adhesive composition and the film-like adhesive is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the thermosetting component (b). When the content of the curing accelerator (c) is equal to or greater than the lower limit, the effect of using the curing accelerator (c) is more pronounced. When the content of the curing accelerator (c) is equal to or less than the upper limit, for example, the effect of suppressing the highly polar curing accelerator (c) from migrating to the adhesive interface with the adherend and segregating in the film-like adhesive under high temperature and high humidity conditions is enhanced, and the reliability of the package obtained using the film-like adhesive is further improved. When using a curing accelerator (c) that is liquid at a temperature of 23°C and does not have a functional group that reacts with the main component contained in the film-like adhesive, it is preferable that the content of the curing accelerator (c) in the adhesive composition and the film-like adhesive satisfies the numerical range separately specified below.

[0257] [Filler (d)] By including the filler (d), the cuttability of the film adhesive by expansion is improved. Furthermore, by including the filler (d), the thermal expansion coefficient of the film adhesive can be easily adjusted, and by optimizing this thermal expansion coefficient for the object to which the film adhesive is applied, the reliability of the package obtained using the film adhesive is improved. Furthermore, by including the filler (d) in the film adhesive, it is possible to reduce the moisture absorption rate of the film adhesive after curing and improve the heat dissipation properties.

[0258] The filler (d) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler. Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride, and the like; beads obtained by spheronizing these inorganic fillers; surface-modified products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, and the like. Among these, the inorganic filler is preferably silica or alumina.

[0259] The adhesive composition and film-like adhesive may contain only one type of filler (d), or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0260] When the filler (d) is used, the ratio of the content of the filler (d) to the total content of all components other than the solvent in the adhesive composition (i.e., the ratio of the content of the filler (d) to the total mass of the film-like adhesive in the film-like adhesive) is preferably 5 to 80 mass%, more preferably 10 to 70 mass%, and particularly preferably 20 to 60 mass%. By having the ratio in such a range, the effect of using the filler (d) can be obtained more significantly.

[0261] [Coupling agent (e)] The film adhesive contains a coupling agent (e) to improve its adhesion and adhesion to the adherend. In addition, the film adhesive contains a coupling agent (e) to improve the water resistance of the cured product without impairing the heat resistance. The coupling agent (e) has a functional group capable of reacting with an inorganic compound or an organic compound.

[0262] The coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional groups of the polymer component (a), the thermosetting component (b), etc., and is more preferably a silane coupling agent.

[0263] The coupling agent (e) contained in the adhesive composition and the film-like adhesive may be one type, or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0264] When a coupling agent (e) is used, the content of the coupling agent (e) in the adhesive composition and the film-like adhesive is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the total content of the polymer component (a) and the thermosetting component (b). When the content of the coupling agent (e) is equal to or greater than the lower limit, the effects of using the coupling agent (e), such as improved dispersibility of the filler (d) in the resin and improved adhesion of the film-like adhesive to the adherend, can be more significantly obtained. When the content of the coupling agent (e) is equal to or less than the upper limit, the generation of outgassing is more suppressed. When using a coupling agent (e) that is liquid at a temperature of 23°C and does not have a functional group that reacts with the main component contained in the film-like adhesive, it is preferable that the content of the coupling agent in the adhesive composition and the film-like adhesive satisfies the numerical range separately specified below.

[0265] [Crosslinking agent (f)] When the polymer component (a) is one having a functional group capable of bonding with other compounds, such as a vinyl group, (meth)acryloyl group, amino group, hydroxyl group, carboxyl group, isocyanate group, etc., such as the above-mentioned acrylic resin, the adhesive composition and film-like adhesive may contain a crosslinking agent (f). The crosslinking agent (f) is a component for bonding the functional group in the polymer component (a) with other compounds to crosslink them, and by crosslinking in this way, the initial adhesive strength and cohesive strength of the film-like adhesive can be adjusted.

[0266] Examples of the crosslinking agent (f) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), and aziridine crosslinking agents (crosslinking agents having an aziridinyl group).

[0267] When an organic polyisocyanate compound is used as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the polymer component (a). When the crosslinking agent (f) has an isocyanate group and the polymer component (a) has a hydroxyl group, a crosslinked structure can be easily introduced into the film-like adhesive by the reaction between the crosslinking agent (f) and the polymer component (a).

[0268] The crosslinking agent (f) contained in the adhesive composition and film-like adhesive may be one type, or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0269] When the crosslinking agent (f) is used, the content of the crosslinking agent (f) in the adhesive composition is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.3 to 5 parts by mass, per 100 parts by mass of the polymer component (a). When the content of the crosslinking agent (f) is equal to or greater than the lower limit, the effect of using the crosslinking agent (f) is more pronounced. When the content of the crosslinking agent (f) is equal to or less than the upper limit, excessive use of the crosslinking agent (f) is suppressed. When using a crosslinking agent (f) that is liquid at a temperature of 23°C and does not have a functional group that reacts with the main component contained in the film-like adhesive, it is preferable that the content of the crosslinking agent in the adhesive composition and the film-like adhesive satisfies the numerical range separately specified below.

[0270] [Energy ray curable resin (g)] By containing the energy ray-curable resin (g) in the adhesive composition and film-like adhesive, the properties of the film-like adhesive can be changed by irradiation with energy rays.

[0271] The energy ray curable resin (g) may be the component (α1), but is preferably not the component (α1).

[0272] The energy ray curable resin (g) is obtained from an energy ray curable compound. The energy ray-curable compound includes, for example, a compound having at least one polymerizable double bond in the molecule, and is preferably an acrylate-based compound having a (meth)acryloyl group.

[0273] The adhesive composition may contain only one type of energy ray-curable resin (g), or may contain two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0274] When an energy ray curable resin (g) is used, the content of the energy ray curable resin (g) in the adhesive composition relative to the total mass of the adhesive composition is preferably 1 to 95 mass%, more preferably 5 to 90 mass%, and particularly preferably 10 to 85 mass%.

[0275] [Photopolymerization initiator (h)] When the adhesive composition and the film-like adhesive contain an energy ray-curable resin (g), they may contain a photopolymerization initiator (h) in order to efficiently proceed with the polymerization reaction of the energy ray-curable resin (g).

[0276] Examples of the photopolymerization initiator (h) in the adhesive composition include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 2,2-dimethoxy-1,2-diphenylethane-1-one; and acylphosphines such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Oxide compounds; sulfide compounds such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone, etc. Examples of the photopolymerization initiator (h) include photosensitizers such as amines.

[0277] The adhesive composition may contain only one type of photopolymerization initiator (h), or may contain two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0278] When a photopolymerization initiator (h) is used, the content of the photopolymerization initiator (h) in the adhesive composition is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass, per 100 parts by mass of the energy ray-curable resin (g). When using a photopolymerization initiator (h) that is liquid at a temperature of 23°C and does not have a functional group that reacts with the main component contained in the film-like adhesive, it is preferable that the content of this photopolymerization initiator in the adhesive composition and the film-like adhesive satisfy the numerical range separately specified below.

[0279] [General purpose additives (i)] The general-purpose additive (i) may be a known one and may be arbitrarily selected depending on the purpose, and is not particularly limited. Preferred examples thereof include plasticizers, antistatic agents, antioxidants, colorants (dyes, pigments), gettering agents, and the like.

[0280] The adhesive composition and the film-like adhesive may contain only one type of general-purpose additive (i), or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0281] The contents of the adhesive composition and the film-like adhesive are not particularly limited and may be appropriately selected depending on the purpose. When using a general-purpose additive (i) that is liquid at a temperature of 23°C and does not have a functional group that reacts with the main component contained in the film-like adhesive, it is preferable that the content of the general-purpose additive in the adhesive composition and the film-like adhesive satisfy the numerical range separately specified below.

[0282] [solvent] The adhesive composition preferably further contains a solvent. An adhesive composition containing a solvent has good handleability. The solvent is not particularly limited, but preferred examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone. The adhesive composition may contain only one type of solvent, or two or more types. When there are two or more types, the combination and ratio of the solvents can be selected arbitrarily.

[0283] The solvent contained in the adhesive composition is preferably methyl ethyl ketone or the like, since this allows the components contained in the adhesive composition to be mixed more uniformly.

[0284] The content of the solvent in the adhesive composition is not particularly limited and may be appropriately selected depending on, for example, the types of components other than the solvent.

[0285] [Component (α2)] The component (α2) in the adhesive composition and the film-like adhesive is liquid at a temperature of 23° C. In addition, the component (α2) does not have a functional group that reacts with the main component contained in the film-like adhesive (i.e., does not react with the main component). A component that has a functional group that reacts with the main component contained in the film-like adhesive and is liquid at a temperature of 23° C. does not migrate from the film-like adhesive to the intermediate layer by reacting with the main component in the film-like adhesive, and as a result, does not migrate to the pressure-sensitive adhesive layer. In this embodiment, the component (α2) that does not have the functional group and is liquid at a temperature of 23° C., which cannot originally suppress the migration from the film-like adhesive to the pressure-sensitive adhesive layer, is suppressed from the film-like adhesive to the pressure-sensitive adhesive layer, instead of the component that has the functional group and is liquid at a temperature of 23° C. For example, when the main component has a hydroxyl group or an amino group, the functional group that reacts with the main component can be an isocyanate group.

[0286] The component (α2) is not particularly limited as long as it satisfies these conditions, and can be selected arbitrarily according to the purpose. The components contained in the adhesive composition that do not fall under any of the polymer component (a), the filler (d), the energy ray curable resin (g), and the solvent, that is, among the thermosetting components (b) (e.g., the epoxy resin (b1) and the thermosetting agent (b2)), the curing accelerator (c), the coupling agent (e), the crosslinking agent (f), the photopolymerization initiator (h), and the general-purpose additive (i), are liquid at a temperature of 23°C and do not have a functional group that reacts with the main component contained in the film-like adhesive, are the components (α2). Solvents are not usually contained in film-like adhesives. A preferred example of the component (α2) is an epoxy resin (b1).

[0287] The adhesive composition may contain only one type of component (α2), or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0288] When the component (α2) is used, the content of the component (α2) in the adhesive composition can be appropriately adjusted depending on the type of the component (α2). In the adhesive composition and film-like adhesive, the content of component (α2) is preferably 1 to 20 parts by mass per 100 parts by mass of the content of polymer component (a). By making the content equal to or less than the upper limit, migration of component (α2) in the film-like adhesive to the pressure-sensitive adhesive layer is further suppressed. By making the content equal to or more than the lower limit, the effect obtained by using component (α2) is further enhanced.

[0289] In particular, when component (α2) is epoxy resin (b1), the content of component (α2) (epoxy resin (b1)) in the adhesive composition and film-like adhesive is preferably 3 to 17 parts by mass, and more preferably 6 to 14 parts by mass, per 100 parts by mass of the content of polymer component (a). By having the content be equal to or less than the upper limit, migration of component (α2) in the film-like adhesive to the pressure-sensitive adhesive layer is further suppressed, and excessive use of component (α2) is suppressed. By having the content be equal to or more than the lower limit, the effects obtained by using component (α2) are further enhanced.

[0290] The film-like adhesive can be cut well by cooling and expanding it, as described below. That is, the sheet for manufacturing a semiconductor device of this embodiment is suitable for cutting the film-like adhesive by cooling and expanding the film-like adhesive.

[0291] <<Method of manufacturing adhesive composition>> The adhesive composition can be obtained by blending the respective components constituting the adhesive composition. The adhesive composition can be produced, for example, in the same manner as in the case of the pressure-sensitive adhesive composition described above, except that the types of ingredients used are different.

[0292] In the sheet for manufacturing semiconductor device of this embodiment, it is preferable that at least the film-like adhesive contains the component (α1) as a main component, or the pressure-sensitive adhesive layer contains the component (γ1) as a main component. That is, examples of preferred sheets for manufacturing semiconductor device in this embodiment include a sheet for manufacturing semiconductor device in which the film-like adhesive contains the component (α1) as a main component and the pressure-sensitive adhesive layer does not contain the component (γ1) as a main component; a sheet for manufacturing semiconductor device in which the pressure-sensitive adhesive layer contains the component (γ1) as a main component and the film-like adhesive does not contain the component (α1) as a main component; and a sheet for manufacturing semiconductor device in which the film-like adhesive contains the component (α1) as a main component and the pressure-sensitive adhesive layer contains the component (γ1) as a main component. In the sheet for producing semiconductor device, it is more preferable that the film-like adhesive contains the component (α1) as a main component, and the pressure-sensitive adhesive layer contains the component (γ1) as a main component.

[0293] In the sheet for manufacturing semiconductor device of this embodiment, it is more preferable that at least the film-like adhesive contains the component (α1) as a main component, or the pressure-sensitive adhesive layer contains the component (γ1) as a main component, and the components (α1) and (γ1) are acrylic resins having structural units derived from (meth)acrylic acid esters. That is, examples of more preferred sheets for manufacturing semiconductor device in this embodiment include sheets for manufacturing semiconductor device in which the film-like adhesive contains the component (α1) as a main component, the pressure-sensitive adhesive layer does not contain the component (γ1) as a main component, and the component (α1) is an acrylic resin having a structural unit derived from a (meth)acrylic acid ester; sheets for manufacturing semiconductor device in which the pressure-sensitive adhesive layer contains the component (γ1) as a main component, the film-like adhesive does not contain the component (α1) as a main component, and the component (γ1) is an acrylic resin having a structural unit derived from a (meth)acrylic acid ester; and sheets for manufacturing semiconductor device in which the film-like adhesive contains the component (α1) as a main component, the pressure-sensitive adhesive layer contains the component (γ1) as a main component, and the components (α1) and (γ1) are acrylic resins having structural units derived from a (meth)acrylic acid ester. It is further preferred that in the sheet for manufacturing semiconductor device, the film-like adhesive contains the component (α1) as a main component, the pressure-sensitive adhesive layer contains the component (γ1) as a main component, and the components (α1) and (γ1) are acrylic resins having structural units derived from a (meth)acrylic acid ester.

[0294] A preferred example of the sheet for manufacturing a semiconductor device according to the present embodiment includes a substrate, a pressure-sensitive adhesive layer, an intermediate layer, and a film-like adhesive, the pressure-sensitive adhesive layer, the intermediate layer, and the film-like adhesive are laminated in this order on the base material, the intermediate layer contains, as a main component, a non-silicon-based resin (β1) having a weight average molecular weight of 20,000 to 100,000; Furthermore, the film-like adhesive contains a component (α2), and the pressure-sensitive adhesive layer contains a component (γ2), the component (α2) is liquid at a temperature of 23° C. and does not have a functional group that reacts with the main component contained in the film-like adhesive; the component (γ2) is liquid at a temperature of 23° C. and has no functional group that reacts with the main component contained in the pressure-sensitive adhesive layer; The haze of the first test piece in the form of a film having a thickness of 10 μm and made of the non-silicon-based resin (β1) is H(β), When the haze of a film-like second test piece having a thickness of 10 μm and made of a mixture of 100 parts by mass of the non-silicon-based resin (β1) and 10 parts by mass of the component (α2) is H(βα), the H(βα) and H(β) can be calculated by the following formula (X1): (X1) H(βα)-H(β)>7% Fulfilling When the haze of a film-like third test piece having a thickness of 10 μm and made of a mixture of 100 parts by mass of the non-silicon-based resin (β1) and 10 parts by mass of the component (γ2) is H(βγ), the H(βγ) and H(β) can be calculated by the following formula (X2): (X2) H(βγ)-H(β)>7% Fulfilling Furthermore, the film-like adhesive contains as a main component a component (α1) that is solid at a temperature of 23°C, the component (α1) being a polymer component (a), the pressure-sensitive adhesive layer contains as a main component a component (γ1) that is solid at a temperature of 23°C, the component (γ1) being a pressure-sensitive adhesive, The intermediate layer may include a sheet for producing semiconductor device, the non-silicon-based resin (β1) being one or more selected from the group consisting of ethylene-vinyl acetate copolymers and polyolefins. In this sheet for manufacturing a semiconductor device, the intermediate layer may further contain a silicon-based resin.

[0295] Another preferred example of the sheet for manufacturing a semiconductor device according to the present embodiment includes a substrate, a pressure-sensitive adhesive layer, an intermediate layer, and a film-like adhesive, the pressure-sensitive adhesive layer, the intermediate layer, and the film-like adhesive are laminated in this order on the base material, the intermediate layer contains, as a main component, a non-silicon-based resin (β1) having a weight average molecular weight of 20,000 to 100,000; Furthermore, the film-like adhesive contains a component (α2), and the pressure-sensitive adhesive layer contains a component (γ2), the component (α2) is an epoxy resin (b1) that is liquid at a temperature of 23° C. and does not have a functional group that reacts with the main component contained in the film-like adhesive; the component (γ2) is an antistatic agent that is liquid at a temperature of 23° C. and does not have a functional group that reacts with a main component contained in the pressure-sensitive adhesive layer, The haze of the first test piece in the form of a film having a thickness of 10 μm and made of the non-silicon-based resin (β1) is H(β), When the haze of a film-like second test piece having a thickness of 10 μm and made of a mixture of 100 parts by mass of the non-silicon-based resin (β1) and 10 parts by mass of the component (α2) is H(βα), the H(βα) and H(β) can be calculated by the following formula (X1): (X1) H(βα)-H(β)>7% Fulfilling When the haze of a film-like third test piece having a thickness of 10 μm and made of a mixture of 100 parts by mass of the non-silicon-based resin (β1) and 10 parts by mass of the component (γ2) is H(βγ), the H(βγ) and H(β) can be calculated by the following formula (X2): (X2) H(βγ)-H(β)>7% Fulfilling Furthermore, the film-like adhesive contains as a main component a component (α1) that is solid at a temperature of 23°C, the component (α1) being a polymer component (a), the pressure-sensitive adhesive layer contains as a main component a component (γ1) that is solid at a temperature of 23°C, the component (γ1) being a pressure-sensitive adhesive, the intermediate layer contains an ethylene-vinyl acetate copolymer as the non-silicon-based resin (β1), In the film-like adhesive, the content of the epoxy resin (b1) is 1 to 20 parts by mass per 100 parts by mass of the polymer component (a), In the pressure-sensitive adhesive layer, the content of the antistatic agent is 0.1 to 10 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive; In the ethylene-vinyl acetate copolymer, the ratio of the mass of structural units derived from vinyl acetate to the total mass of all structural units is 45 mass % or less. In this sheet for manufacturing semiconductor device, in the ethylene-vinyl acetate copolymer, the ratio of the mass of structural units derived from vinyl acetate to the total mass of all structural units may be 30 mass % or less. In this sheet for manufacturing a semiconductor device, the intermediate layer may further contain a silicon-based resin, in which case the content of the silicon-based resin in the intermediate layer may be 0.01 to 10 mass % relative to the total mass of the intermediate layer.

[0296] Yet another example of a preferable sheet for manufacturing a semiconductor device according to the present embodiment includes a substrate, a pressure-sensitive adhesive layer, an intermediate layer, and a film-like adhesive, the pressure-sensitive adhesive layer, the intermediate layer, and the film-like adhesive are laminated in this order on the base material, the intermediate layer contains, as a main component, a non-silicon-based resin (β1) having a weight average molecular weight of 20,000 to 100,000; Furthermore, the film-like adhesive contains a component (α2), and the pressure-sensitive adhesive layer contains a component (γ2), the component (α2) is an epoxy resin (b1) that is liquid at a temperature of 23° C. and does not have a functional group that reacts with the main component contained in the film-like adhesive; the component (γ2) is an antistatic agent that is liquid at a temperature of 23° C. and does not have a functional group that reacts with a main component contained in the pressure-sensitive adhesive layer, The haze of the first test piece in the form of a film having a thickness of 10 μm and made of the non-silicon-based resin (β1) is H(β), When the haze of a film-like second test piece having a thickness of 10 μm and made of a mixture of 100 parts by mass of the non-silicon-based resin (β1) and 10 parts by mass of the component (α2) is H(βα), the H(βα) and H(β) can be calculated by the following formula (X1): (X1) H(βα)-H(β)>7% Fulfilling When the haze of a film-like third test piece having a thickness of 10 μm and made of a mixture of 100 parts by mass of the non-silicon-based resin (β1) and 10 parts by mass of the component (γ2) is H(βγ), the H(βγ) and H(β) can be calculated by the following formula (X2): (X2) H(βγ)-H(β)>7% Fulfilling Furthermore, the film-like adhesive contains as a main component a component (α1) that is solid at a temperature of 23°C, the component (α1) being a polymer component (a), the pressure-sensitive adhesive layer contains as a main component a component (γ1) that is solid at a temperature of 23°C, the component (γ1) being a pressure-sensitive adhesive, and the polymer component (a) and the pressure-sensitive adhesive are acrylic resins having structural units derived from a (meth)acrylic acid ester, the intermediate layer contains an ethylene-vinyl acetate copolymer as the non-silicon-based resin (β1), In the film-like adhesive, the content of the epoxy resin (b1) is 1 to 20 parts by mass per 100 parts by mass of the polymer component (a), In the pressure-sensitive adhesive layer, the content of the antistatic agent is 0.1 to 10 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive; In the ethylene-vinyl acetate copolymer, the ratio of the mass of structural units derived from vinyl acetate to the total mass of all structural units is 45 mass % or less. In this sheet for manufacturing semiconductor device, in the ethylene-vinyl acetate copolymer, the ratio of the mass of structural units derived from vinyl acetate to the total mass of all structural units may be 30 mass % or less. In this sheet for manufacturing semiconductor device, the intermediate layer may further contain polydimethylsiloxane, and in that case, the content of the polydimethylsiloxane in the intermediate layer may be 0.01 to 10 mass % relative to the total mass of the intermediate layer.

[0297] ◇ Manufacturing method of sheets for manufacturing semiconductor device The semiconductor device manufacturing sheet can be manufactured by laminating the above-mentioned layers in a corresponding positional relationship. The method of forming each layer is as described above.

[0298] For example, the semiconductor device manufacturing sheet can be manufactured by preparing the base material, pressure-sensitive adhesive layer, intermediate layer and film-like adhesive in advance, and laminating these in the following order: base material, pressure-sensitive adhesive layer, intermediate layer and film-like adhesive. However, this is just one example of a method for producing a sheet for manufacturing a semiconductor device.

[0299] The semiconductor device manufacturing sheet can also be manufactured, for example, by preparing two or more intermediate laminates in advance, each having a structure in which a plurality of layers are laminated, and bonding these intermediate laminates together. The structure of the intermediate laminate can be selected as appropriate. For example, a first intermediate laminate (corresponding to the support sheet) having a structure in which a base material and an adhesive layer are laminated, and a second intermediate laminate having a structure in which an intermediate layer and a film-like adhesive are laminated are prepared in advance, and the adhesive layer in the first intermediate laminate and the intermediate layer in the second intermediate laminate are bonded together to manufacture the semiconductor device manufacturing sheet. However, this is also just one example of the method for producing a sheet for producing semiconductor device.

[0300] When the sheet for manufacturing a semiconductor device is manufactured as shown in Fig. 1, in which the area of ​​the first side of the intermediate layer and the area of ​​the first side of the film-like adhesive are both smaller than the areas of the first side of the pressure-sensitive adhesive layer and the first side of the base material, a step of processing the intermediate layer and the film-like adhesive to a desired size may be added at any stage of the above-mentioned manufacturing method. For example, in the manufacturing method using the second intermediate laminate, a sheet for manufacturing a semiconductor device may be manufactured by adding a step of processing the intermediate layer and the film-like adhesive in the second intermediate laminate to a desired size.

[0301] When manufacturing a sheet for manufacturing semiconductor device having a release film on the film-like adhesive, for example, the film-like adhesive may be prepared on the release film, and the remaining layers may be laminated while maintaining this state to produce the sheet for manufacturing semiconductor device, or the base material, pressure-sensitive adhesive layer, intermediate layer, and film-like adhesive may all be laminated, and then the release film may be laminated on the film-like adhesive to produce the sheet for manufacturing semiconductor device. The release film may be removed at a necessary stage before the sheet for manufacturing semiconductor device is used.

[0302] A sheet for manufacturing a semiconductor device that has another layer that does not fall into any of the following categories: a substrate, an adhesive layer, an intermediate layer, a film-like adhesive, and a release film, can be manufactured by adding a step of forming and laminating this other layer at an appropriate time in the above-mentioned manufacturing method.

[0303] However, in order to manufacture the sheet for manufacturing semiconductor device, it is necessary to select a combination of the non-silicon-based resin (β1) in the film-like adhesive and the component (α2) in the intermediate layer that satisfies the above formula (X1), or to select a combination of the non-silicon-based resin (β1) in the film-like adhesive and the component (γ2) in the pressure-sensitive adhesive layer that satisfies the above formula (X2).

[0304] That is, the present embodiment is a method for producing a sheet for manufacturing a semiconductor device, The sheet for manufacturing a semiconductor device includes a substrate, a pressure-sensitive adhesive layer, an intermediate layer, and a film-like adhesive, the pressure-sensitive adhesive layer, the intermediate layer, and the film-like adhesive are laminated in this order on the base material, the intermediate layer contains, as a main component, a non-silicon-based resin (β1) having a weight average molecular weight of 20,000 to 100,000; Furthermore, at least the film-like adhesive contains a component (α2) or the pressure-sensitive adhesive layer contains a component (γ2), the component (α2) is liquid at a temperature of 23° C. and does not have a functional group that reacts with the main component contained in the film-like adhesive; the component (γ2) is liquid at a temperature of 23° C. and has no functional group that reacts with the main component contained in the pressure-sensitive adhesive layer; The haze of the first test piece in the form of a film having a thickness of 10 μm and made of the non-silicon-based resin (β1) is H(β), In the case where the film-like adhesive contains the component (α2), when the haze of a film-like second test piece having a thickness of 10 μm and made of a mixture of 100 parts by mass of the non-silicon-based resin (β1) and 10 parts by mass of the component (α2) is H(βα), H(βα) and H(β) can be calculated by the following formula (X1): (X1) H(βα)-H(β)>7% Fulfilling In the case where the pressure-sensitive adhesive layer contains the component (γ2), when the haze of a film-like third test piece having a thickness of 10 μm and made of a mixture of 100 parts by mass of the non-silicon-based resin (β1) and 10 parts by mass of the component (γ2) is H(βγ), the H(βγ) and H(β) can be calculated by the following formula (X2): (X2) H(βγ)-H(β)>7% Fulfilling The manufacturing method includes either or both of a film-like adhesive preparation step of preparing the film-like adhesive containing the component (α2) and a pressure-sensitive adhesive layer preparation step of preparing the pressure-sensitive adhesive layer containing the component (γ2).

[0305] Thus, the manufacturing method for a semiconductor device manufacturing sheet of this embodiment may be a manufacturing method that has the film-like adhesive manufacturing step but does not have the pressure-sensitive adhesive layer manufacturing step, or a manufacturing method that has the pressure-sensitive adhesive layer manufacturing step but does not have the film-like adhesive manufacturing step, or a manufacturing method that has both the film-like adhesive manufacturing step and the pressure-sensitive adhesive layer manufacturing step, depending on the desired configuration of the semiconductor device manufacturing sheet. In the film-like adhesive preparation step, a film-like adhesive is prepared using the adhesive composition containing component (α2). In the pressure-sensitive adhesive layer preparation step, a pressure-sensitive adhesive layer is prepared using the pressure-sensitive adhesive composition containing component (γ2).

[0306] ◇Manufacturing method for semiconductor chips with film-like adhesive (Method of using sheets for manufacturing semiconductor device) The sheet for manufacturing a semiconductor device can be used when manufacturing a semiconductor chip with a film-like adhesive in the process of manufacturing a semiconductor device. Hereinafter, the method for producing a semiconductor chip with a film-like adhesive (method for using the sheet for producing semiconductor device) will be described in detail with reference to the drawings.

[0307] 3A, 3B, and 3C are cross-sectional views for explaining an example of a method for manufacturing a semiconductor chip with a film-like adhesive, and show a manufacturing method in which a semiconductor device manufacturing sheet is attached to a semiconductor wafer before use. In this method, the semiconductor device manufacturing sheet is used as a dicing die bonding sheet. Here, an example will be explained in which the semiconductor device manufacturing sheet 101 shown in FIG. 1 is used.

[0308] First, as shown in FIG. 3A, sheet 101 for manufacturing semiconductor device from which release film 15 has been removed is heated, and film adhesive 14 therein is attached to rear surface 9b' of semiconductor wafer 9'. Reference numeral 9a' denotes a surface of the semiconductor wafer 9' on which circuits are formed.

[0309] The heating temperature during application of the semiconductor device manufacturing sheet 101 is not particularly limited, but is preferably 40 to 70° C. in order to further improve the thermal application stability of the semiconductor device manufacturing sheet 101 .

[0310] Width W of the intermediate layer 13 in the semiconductor device manufacturing sheet 101 13 and the width W of the film adhesive 14 14 The maximum value of each of these is the width W of the semiconductor wafer 9'. 9’ It is preferable that the value is exactly the same as the maximum value of , or that the value is not the same but is approximately the same with a small error.

[0311] For example, the width W of the semiconductor wafer 9′ 9’ When the maximum value of is 150 mm, the width W of the intermediate layer 13 13 and the width W of the film adhesive 14 14 The maximum value of is preferably 150 to 160 mm, and the width W of the semiconductor wafer 9' is 9’ When the maximum value of is 200 mm, the width W of the intermediate layer 13 13 and the width W of the film adhesive 14 14 The maximum value of is preferably 200 to 210 mm, and the width W of the semiconductor wafer 9' is 9’ When the maximum value of is 300 mm, the width W of the intermediate layer 13 13 and the width W of the film adhesive 14 14 The maximum value is preferably 300 to 310 mm. Thus, in this embodiment, the width W of the intermediate layer 13 13 and the width W of the semiconductor wafer 9' 9’ The difference between the maximum value of and the width W of the film adhesive 14 14 and the width W of the semiconductor wafer 9' 9’ The maximum value of and the difference between may be 0 to 10 mm. Here, the width W of the semiconductor wafer 9′ 9’ For example, it means the width of a semiconductor wafer 9' in a direction parallel to its back surface 9b'.

[0312] Next, the laminate of the semiconductor device manufacturing sheet 101 and the semiconductor wafer 9' obtained above is cut with a blade from the circuit forming surface 9a' side of the semiconductor wafer 9' (blade dicing is performed) to divide the semiconductor wafer 9' and cut the film-like adhesive 14.

[0313] Blade dicing can be performed by a known method. For example, the region (the non-laminated region) near the periphery of the first surface 12a of the pressure-sensitive adhesive layer 12 in the sheet 101 for manufacturing a semiconductor device, where the intermediate layer 13 and the film-like adhesive 14 are not laminated, can be fixed to a jig such as a ring frame (not shown), and then the semiconductor wafer 9' can be divided and the film-like adhesive 14 can be cut using a blade.

[0314] 3B, a plurality of semiconductor chips 914 with a film-like adhesive are obtained, each of which includes a semiconductor chip 9 and a cut film-like adhesive 140 provided on its back surface 9b. These semiconductor chips 914 with a film-like adhesive are aligned and fixed on the intermediate layer 13 in the laminated sheet 10, constituting a group 910 of semiconductor chips with a film-like adhesive. A back surface 9b of the semiconductor chip 9 corresponds to a back surface 9b' of the semiconductor wafer 9'. In Fig. 3B, reference numeral 9a denotes a circuit forming surface of the semiconductor chip 9, which corresponds to a circuit forming surface 9a' of the semiconductor wafer 9'.

[0315] During blade dicing, the semiconductor wafer 9' is divided by cutting into it across its entire thickness, and the semiconductor device manufacturing sheet 101 is cut into the film-like adhesive 14 across its entire thickness by cutting from the first surface 14a of the film-like adhesive 14 to the area halfway through the intermediate layer 13, preferably without cutting into the pressure-sensitive adhesive layer 12. That is, during blade dicing, it is preferable that the blade cuts into the laminate of the semiconductor device manufacturing sheet 101 and the semiconductor wafer 9' in the stacking direction from the circuit formation surface 9a' of the semiconductor wafer 9' to at least the first surface 13a of the intermediate layer 13, but not to the surface opposite the first surface 13a of the intermediate layer 13 (i.e., the contact surface with the adhesive layer 12).

[0316] In this step, it is easy to prevent the blade from reaching the substrate 11, thereby suppressing the generation of cutting chips from the substrate 11. Furthermore, since the main component of the intermediate layer 13 cut by the blade is a non-silicon-based resin (β1) having a weight average molecular weight of 20,000 to 100,000, in particular, a weight average molecular weight of 100,000 or less, the generation of cutting chips from the intermediate layer 13 can also be suppressed.

[0317] The conditions for the blade dicing may be appropriately adjusted depending on the purpose, and are not particularly limited. Generally, the rotation speed of the blade is preferably 15,000 to 50,000 rpm, and the movement speed of the blade is preferably 5 to 85 mm / sec, and may be 5 to 75 mm / sec.

[0318] After blade dicing, the semiconductor chip 914 with the film-like adhesive is detached from the intermediate layer 13 in the laminated sheet 10 and picked up, as shown in Fig. 3C. Here, the case where the semiconductor chip 914 with the film-like adhesive is detached in the direction of arrow P using detachment means 7 such as a vacuum collet is shown. Note that the detachment means 7 is not shown in cross section here. The semiconductor chip 914 with the film-like adhesive attached can be picked up by a known method.

[0319] When the silicon concentration on the first surface 13a of the intermediate layer 13 is between 1 and 20%, the semiconductor chip 914 with the film adhesive can be picked up more easily. When the intermediate layer 13 contains, for example, an ethylene-vinyl acetate copolymer which is the non-silicon-based resin (β1) and a siloxane-based compound which is the additive, and the content of the ethylene-vinyl acetate copolymer in the intermediate layer relative to the total mass of the intermediate layer is 90 to 99.99 mass%, and the content of the siloxane-based compound in the intermediate layer relative to the total mass of the intermediate layer is 0.01 to 10 mass%, the semiconductor chip 914 with the film-like adhesive can be picked up more easily.

[0320] A preferred embodiment of the method for producing a semiconductor chip with a film-like adhesive described above is, for example, a method for producing a semiconductor chip with a film-like adhesive using a sheet for manufacturing a semiconductor device, The semiconductor chip with a film-like adhesive includes a semiconductor chip and a film-like adhesive provided on a back surface of the semiconductor chip, The sheet for manufacturing a semiconductor device includes a substrate, a pressure-sensitive adhesive layer, an intermediate layer, and a film-like adhesive, the pressure-sensitive adhesive layer, the intermediate layer, and the film-like adhesive are laminated in this order on the base material, the intermediate layer contains, as a main component, a non-silicon-based resin (β1) having a weight average molecular weight of 20,000 to 100,000; Furthermore, at least the film-like adhesive contains a component (α2) or the pressure-sensitive adhesive layer contains a component (γ2), the component (α2) is liquid at a temperature of 23° C. and does not have a functional group that reacts with the main component contained in the film-like adhesive; the component (γ2) is liquid at a temperature of 23° C. and has no functional group that reacts with the main component contained in the pressure-sensitive adhesive layer; The haze of a 10 μm-thick film specimen made of the non-silicon-based resin (β1) is H(β), In the case where the film-like adhesive contains the component (α2), when the haze of a film-like second test piece having a thickness of 10 μm and made of a mixture of 100 parts by mass of the non-silicon-based resin (β1) and 10 parts by mass of the component (α2) is H(βα), H(βα) and H(β) can be calculated by the following formula (X1): (X1) H(βα)-H(β)>7% Fulfilling In the case where the pressure-sensitive adhesive layer contains the component (γ2), when the haze of a film-like third test piece having a thickness of 10 μm and made of a mixture of 100 parts by mass of the non-silicon-based resin (β1) and 10 parts by mass of the component (γ2) is H(βγ), the H(βγ) and H(β) can be calculated by the following formula (X2): (X2) H(βγ)-H(β)>7% Fulfilling The manufacturing method includes a step of attaching the film-like adhesive in the semiconductor device manufacturing sheet to a back surface of the semiconductor wafer while heating the sheet; a step of cutting the semiconductor wafer to which the film-like adhesive has been applied from the circuit formation surface side across the entire thickness direction to divide the semiconductor chips, and cutting the semiconductor device manufacturing sheet in the thickness direction from the film-like adhesive side to an area halfway through the intermediate layer to cut the film-like adhesive, but not cutting into the pressure-sensitive adhesive layer, thereby obtaining a group of semiconductor chips with a film-like adhesive in which a plurality of the semiconductor chips with the film-like adhesive are aligned on the intermediate layer; and a step of separating the semiconductor chip with the film-like adhesive from the intermediate layer and picking it up (sometimes referred to as "manufacturing method 1" in this specification).

[0321] Figures 4A, 4B, and 4C are cross-sectional views for illustrating an example of a method for manufacturing semiconductor chips for which a semiconductor device manufacturing sheet is used, and show the case where semiconductor chips are manufactured by dicing a semiconductor wafer, which involves the formation of a modified layer. 5A, 5B, and 5C are cross-sectional views for explaining another example of a method for manufacturing a semiconductor chip with a film-like adhesive, and show a manufacturing method in which a semiconductor device manufacturing sheet is attached to a semiconductor chip before use. In this method, the semiconductor device manufacturing sheet is used as a die bonding sheet. Here, the method of use will be explained by taking the semiconductor device manufacturing sheet 101 shown in FIG. 1 as an example.

[0322] First, prior to using the sheet 101 for manufacturing semiconductor device, as shown in FIG. 4A, a semiconductor wafer 9' is prepared, and a backgrind tape (sometimes called a "surface protection tape") 8 is attached to its circuit formation surface 9a'. In FIG. 4A, symbol W 9’ indicates the width of the semiconductor wafer 9'.

[0323] Next, a laser beam (not shown) is irradiated so as to be focused at a focal point set inside the semiconductor wafer 9', thereby forming a modified layer 90' inside the semiconductor wafer 9' as shown in FIG. 4B. The laser light is preferably applied to the semiconductor wafer 9' from the back surface 9b' side of the semiconductor wafer 9'.

[0324] The position of the focus at this time is the planned dividing (dicing) position of the semiconductor wafer 9', and is set so that the desired size, shape and number of semiconductor chips can be obtained from the semiconductor wafer 9'.

[0325] Next, a grinder (not shown) is used to grind the back surface 9b' of the semiconductor wafer 9'. This adjusts the thickness of the semiconductor wafer 9' to a desired value, and the grinding force applied to the semiconductor wafer 9' at this time is used to divide the semiconductor wafer 9' at the portion where the modified layer 90' is formed, to produce a plurality of semiconductor chips 9 as shown in FIG. 4C.

[0326] The modified layer 90' of the semiconductor wafer 9' is different from other parts of the semiconductor wafer 9' in that it has been altered by the irradiation of the laser light and has a weakened strength. Therefore, when a force is applied to the semiconductor wafer 9' on which the modified layer 90' has been formed, the force is applied to the modified layer 90', and the semiconductor wafer 9' is cracked at the site of the modified layer 90', and a plurality of semiconductor chips 9 are obtained.

[0327] By the above steps, semiconductor chips 9 are obtained, which are the targets of use of semiconductor device manufacturing sheet 101. More specifically, this process produces semiconductor chip group 901 in which a plurality of semiconductor chips 9 are aligned and fixed on backgrind tape 8.

[0328] When semiconductor chip group 901 is viewed from above in a planar view, the planar shape formed by connecting the outermost portions of semiconductor chip group 901 (in this specification, such a planar shape may be simply referred to as the "planar shape of the semiconductor chip group") is exactly the same as the planar shape of semiconductor wafer 9' when viewed in a similar planar view, or the differences between these planar shapes are so minor that they can be ignored, and it can be said that the planar shape of semiconductor chip group 901 is generally the same as the planar shape of semiconductor wafer 9'. Therefore, the width of the planar shape of the semiconductor chip group 901 is, as shown in FIG. 4C, the width W 9’ The maximum width of the planar shape of the semiconductor chip group 901 is equal to the width W 9’ can be considered to be the same as the maximum value of

[0329] Note that, here, we show a case where semiconductor chips 9 can be produced as intended from the semiconductor wafer 9'; however, depending on the conditions for grinding the back surface 9b' of the semiconductor wafer 9', some areas of the semiconductor wafer 9' may not be divided into semiconductor chips 9.

[0330] Next, the semiconductor chips 9 (semiconductor chip group 901) obtained above are used to manufacture semiconductor chips with a film-like adhesive. 5A, one semiconductor device manufacturing sheet 101 from which release film 15 has been removed is heated and film-like adhesive 14 therein is attached to the back surfaces 9b of all the semiconductor chips 9 in semiconductor chip group 901. The object to which film-like adhesive 14 is attached at this time may be a semiconductor wafer that has not been completely divided.

[0331] Width W of the intermediate layer 13 in the semiconductor device manufacturing sheet 101 13 and the width W of the film adhesive 14 14 The maximum value of each of these is the width W of the semiconductor wafer 9'. 9’ It is preferable that the width is exactly the same as the maximum value of the width of the semiconductor chip group 901 (in other words, the width of the semiconductor chip group 901), or that the width is not the same but is approximately the same with a slight error.

[0332] That is, the width W of the intermediate layer 13 13 The relationship between the maximum value of and the maximum width of the semiconductor chip group 901 is determined by the width W 13 and the width W of the semiconductor wafer 9' 9’ The relationship between the maximum value of and the width W of the film adhesive 14 may be the same as that of. 14 and the maximum width of the semiconductor chip group 901, the relationship between the maximum value of 14 and the width W of the semiconductor wafer 9' 9’ The relationship between the maximum value of and may be the same as that between.

[0333] At this time, the attachment of the film-like adhesive 14 (sheet 101 for manufacturing a semiconductor device) to the semiconductor chip group 901 can be carried out in the same manner as the attachment of the film-like adhesive 14 (sheet 101 for manufacturing a semiconductor device) to the semiconductor wafer 9' in the manufacturing method 1, except that the semiconductor chip group 901 is used instead of the semiconductor wafer 9'.

[0334] Next, the backgrind tape 8 is removed from the semiconductor chip group 901 in this fixed state. Then, as shown in FIG. 5B, the semiconductor device manufacturing sheet 101 (film-like adhesive 14) is expanded by being stretched in a direction parallel to its surface (for example, the first surface 12a of the pressure-sensitive adhesive layer 12) while being cooled. Here, the direction in which the semiconductor device manufacturing sheet 101 expands is indicated by an arrow E1. By expanding in this manner, the film-like adhesive 14 is cut along the outer periphery of the semiconductor chip 9.

[0335] This process produces a plurality of semiconductor chips 914 with a film-like adhesive, each of which includes a semiconductor chip 9 and a cut film-like adhesive 140 provided on the back surface 9b of the semiconductor chip 9. These semiconductor chips 914 with a film-like adhesive are aligned and fixed on the intermediate layer 13 in the laminated sheet 10, constituting a group 910 of semiconductor chips with a film-like adhesive. The semiconductor chip 914 with film-like adhesive and the group of semiconductor chips 910 with film-like adhesive obtained here are both substantially the same as the semiconductor chip 914 with film-like adhesive and the group of semiconductor chips 910 with film-like adhesive obtained by the manufacturing method 1 described above.

[0336] As explained above, if a portion of the semiconductor wafer 9' is not divided into semiconductor chips 9 when the semiconductor wafer 9' is divided, this portion will be divided into semiconductor chips by performing this process.

[0337] The sheet 101 for manufacturing semiconductor device (film-like adhesive 14) is preferably expanded at a temperature of −5 to 5° C. By cooling and expanding the sheet 101 for manufacturing semiconductor device in this manner (performing cool expansion), the film-like adhesive 14 can be cut more easily and with higher accuracy.

[0338] The sheet 101 for manufacturing a semiconductor device (film-like adhesive) can be expanded by a known method. For example, the sheet 101 for manufacturing a semiconductor device can be expanded by fixing the area (the non-laminated area) near the periphery of the first surface 12a of the pressure-sensitive adhesive layer 12 in the sheet 101 for manufacturing a semiconductor device, where the intermediate layer 13 and the film-like adhesive 14 are not laminated, to a jig such as a ring frame (not shown), and then pushing up the entire area of ​​the sheet 101 for manufacturing a semiconductor device, where the intermediate layer 13 and the film-like adhesive 14 are laminated, from the base material 11 side in the direction from the base material 11 toward the pressure-sensitive adhesive layer 12.

[0339] In Figure 5B, the non-laminated region of the first surface 12a of the adhesive layer 12, where the intermediate layer 13 and the film-like adhesive 14 are not laminated, is approximately parallel to the first surface 13a of the intermediate layer 13. However, as described above, when the semiconductor device manufacturing sheet 101 is expanded by being pushed up, the non-laminated region includes an inclined surface whose height decreases in the opposite direction to the pushing-up direction as it approaches the outer periphery of the adhesive layer 12.

[0340] In this process, since the semiconductor device manufacturing sheet 101 has an intermediate layer 13 (in other words, the film-like adhesive 14 before cutting is provided on the intermediate layer 13), the film-like adhesive 14 can be cut precisely at the desired location (in other words, along the outer periphery of the semiconductor chip 9), thereby preventing poor cutting.

[0341] After the expansion, as shown in FIG. 5C, the semiconductor chip 914 with the film-like adhesive attached is separated from the intermediate layer 13 in the laminated sheet 10 and picked up. The pick-up at this time can be performed in the same manner as the pick-up in the manufacturing method 1 described above, and the pick-up suitability is also the same as that in the manufacturing method 1.

[0342] For example, in this step too, when the silicon concentration ratio on the first surface 13a of the intermediate layer 13 is 1 to 20%, the semiconductor chip 914 with the film adhesive can be picked up more easily. Furthermore, when the intermediate layer 13 contains, for example, an ethylene-vinyl acetate copolymer which is the non-silicon-based resin and a siloxane-based compound which is the additive, and the content of the ethylene-vinyl acetate copolymer in the intermediate layer relative to the total mass of the intermediate layer is 90 to 99.99 mass%, and the content of the siloxane-based compound in the intermediate layer relative to the total mass of the intermediate layer is 0.01 to 10 mass%, the semiconductor chip 914 with the film-like adhesive can be picked up more easily.

[0343] A preferred embodiment of the method for producing a semiconductor chip with a film-like adhesive described above is, for example, a method for producing a semiconductor chip with a film-like adhesive using a sheet for manufacturing a semiconductor device, The semiconductor chip with a film-like adhesive includes a semiconductor chip and a film-like adhesive provided on a back surface of the semiconductor chip, The sheet for manufacturing a semiconductor device includes a substrate, a pressure-sensitive adhesive layer, an intermediate layer, and a film-like adhesive, the pressure-sensitive adhesive layer, the intermediate layer, and the film-like adhesive are laminated in this order on the base material, the intermediate layer contains, as a main component, a non-silicon-based resin (β1) having a weight average molecular weight of 20,000 to 100,000; Furthermore, at least the film-like adhesive contains a component (α2) or the pressure-sensitive adhesive layer contains a component (γ2), the component (α2) is liquid at a temperature of 23° C. and does not have a functional group that reacts with the main component contained in the film-like adhesive; the component (γ2) is liquid at a temperature of 23° C. and has no functional group that reacts with the main component contained in the pressure-sensitive adhesive layer; The haze of a 10 μm-thick film specimen made of the non-silicon-based resin (β1) is H(β), In the case where the film-like adhesive contains the component (α2), when the haze of a film-like second test piece having a thickness of 10 μm and made of a mixture of 100 parts by mass of the non-silicon-based resin (β1) and 10 parts by mass of the component (α2) is H(βα), H(βα) and H(β) can be calculated by the following formula (X1): (X1) H(βα)-H(β)>7% Fulfilling In the case where the pressure-sensitive adhesive layer contains the component (γ2), when the haze of a film-like third test piece having a thickness of 10 μm and made of a mixture of 100 parts by mass of the non-silicon-based resin (β1) and 10 parts by mass of the component (γ2) is H(βγ), the H(βγ) and H(β) can be calculated by the following formula (X2): (X2) H(βγ)-H(β)>7% Fulfilling The manufacturing method includes a step of forming a modified layer inside the semiconductor wafer by irradiating a laser beam so as to be focused at a focal point set inside the semiconductor wafer; a step of grinding the back surface of the semiconductor wafer after the modified layer is formed, and dividing the semiconductor wafer at the portion where the modified layer is formed by utilizing a grinding force applied to the semiconductor wafer, thereby obtaining a group of semiconductor chips in a state where a plurality of the semiconductor chips are aligned; a step of attaching the film-like adhesive therein to the backsides of all of the semiconductor chips in the group of semiconductor chips while heating the sheet for manufacturing semiconductor device; a step of stretching the semiconductor device manufacturing sheet after being attached to the semiconductor chip in a direction parallel to the surface while cooling, thereby cutting the film-like adhesive along the outer periphery of the semiconductor chip, thereby obtaining a group of semiconductor chips with a film-like adhesive in a state where a plurality of the semiconductor chips with the film-like adhesive are aligned on the intermediate layer; and a step of separating the semiconductor chip with the film-like adhesive from the intermediate layer and picking it up (sometimes referred to as "production method 2" in this specification).

[0344] Up to this point, in both manufacturing method 1 and manufacturing method 2, the manufacturing method of the semiconductor chip with the film-like adhesive has been described using the semiconductor device manufacturing sheet 101 shown in Fig. 1 as an example, but the semiconductor chip with the film-like adhesive can also be manufactured in the same manner when using other sheets for manufacturing semiconductor device according to this embodiment. In that case, if necessary, other steps may be appropriately added based on the difference in configuration between this sheet for manufacturing semiconductor device and the sheet for manufacturing semiconductor device 101 to manufacture the semiconductor chip with the film-like adhesive.

[0345] Not limited to the cases of manufacturing method 1 and manufacturing method 2, after obtaining the group of semiconductor chips with film-like adhesive, before picking up the semiconductor chips with film-like adhesive, the laminated sheet may be expanded in a direction parallel to the surface (first surface) of the pressure-sensitive adhesive layer facing the intermediate layer, and further, while maintaining this state, the peripheral portion of the laminated sheet on which the semiconductor chips with film-like adhesive (group of semiconductor chips with film-like adhesive) are not placed may be heated. In this way, the distance between adjacent semiconductor chips, i.e., the kerf width, can be maintained sufficiently wide and highly uniform on the laminated sheet while the peripheral portion is shrunk, and the semiconductor chips with the film-like adhesive attached can be picked up more easily. EXAMPLES

[0346] The present invention will be described in more detail below with reference to specific examples, although the present invention is not limited to the following examples.

[0347] <<Raw materials for manufacturing adhesive composition>> The raw materials used in producing the adhesive composition are shown below. [Polymer component (a)] (a)-1: An acrylic resin (weight average molecular weight: 800,000, glass transition temperature: 9° C.) obtained by copolymerizing methyl acrylate (95 parts by mass) and 2-hydroxyethyl acrylate (5 parts by mass). [Epoxy resin (b1)] (b1)-1: Bisphenol A type epoxy resin that is liquid at 23°C ("jER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184-194g / eq, number average molecular weight 370, viscosity at 25°C 120-150P (12-15Pa s)) [Thermal hardener (b2)] (b2)-1: Aralkyl-type phenolic resin (Mitsui Chemicals, Inc., "Milex XLC-4L", number average molecular weight 1100, softening point 63°C) [Filler (d)] (d)-1: Spherical silica ("YA050C-MJE" manufactured by Admatechs Co., Ltd., average particle size 50 nm, methacrylsilane-treated product) [Coupling agent (e)] (e)-1: Silane coupling agent, 3-glycidoxypropylmethyldiethoxysilane ("KBE-402" manufactured by Shin-Etsu Silicone Co., Ltd.) [Crosslinking agent (f)] (f)-1: Tolylene diisocyanate crosslinking agent ("Coronate L" manufactured by Tosoh Corporation)

[0348] [Example 1] <<Manufacturing of sheets for manufacturing semiconductor devices>> <Production of substrate> Low-density polyethylene (LDPE, "Sumikathene L705" manufactured by Sumitomo Chemical Co., Ltd.) was melted using an extruder, the molten material was extruded using the T-die method, and the extrudate was biaxially stretched using a cooling roll to obtain an LDPE substrate (thickness 110 μm).

[0349] <Preparation of adhesive layer> A non-energy ray curable adhesive composition was produced, which contained an acrylic resin (Olivine BPS 6367X, manufactured by Toyochem Co., Ltd.) (100 parts by mass) as the adhesive resin (I-1a), a crosslinking agent (BXX 5640, manufactured by Toyochem Co., Ltd., a xylylene diisocyanate-based crosslinking agent) (1 part by mass), and an amine-based ionic liquid (IL-A2, manufactured by Koei Chemical Co., Ltd.) (3 parts by mass) that is liquid at 23°C as an antistatic agent.

[0350] Next, a release film made of polyethylene terephthalate on one side of which a release treatment had been performed by silicone treatment was used, and the adhesive composition obtained above was applied to the release-treated surface, followed by heating and drying at 100°C for 2 minutes to produce a non-energy ray-curable adhesive layer (thickness 10 μm).

[0351] <Preparation of intermediate layer> At room temperature, 15 g of ethylene-vinyl acetate copolymer (EVA, weight average molecular weight 30,000, content of structural units derived from vinyl acetate 25% by mass) was dissolved in 85 g of tetrahydrofuran, and 1.5 g of a siloxane-based compound (polydimethylsiloxane, "BYK-333" manufactured by BYK Japan, number of structural units represented by the formula "-Si(-CH3)2-O-" in one molecule is 45 to 230) was added to the resulting solution and stirred to prepare a composition for forming an intermediate layer.

[0352] A release film made of polyethylene terephthalate on one side of which a release treatment had been performed by silicone treatment was used, and the composition for forming an intermediate layer obtained above was applied to the release-treated surface, followed by heating and drying at 70°C for 5 minutes to produce an intermediate layer (thickness 20 μm).

[0353] <Preparation of film adhesive> A thermosetting adhesive composition was produced containing polymer component (a)-1 (100 parts by mass), epoxy resin (b1)-1 (10 parts by mass), thermosetting agent (b2)-1 (1.5 parts by mass), filler (d)-1 (75 parts by mass), coupling agent (e)-1 (0.5 parts by mass), and crosslinker (f)-1 (0.5 parts by mass). Note that all contents shown here are the contents of the target material excluding the solvent.

[0354] Next, a release film made of polyethylene terephthalate, one side of which had been treated for release by silicone treatment, was used, and the adhesive composition obtained above was applied to the release-treated surface, followed by heating and drying at 80°C for 2 minutes to produce a thermosetting film-like adhesive (thickness 7 μm).

[0355] <Production of Sheets for Manufacturing Semiconductor Device> The exposed surface of the adhesive layer obtained above, opposite the side having the release film, was bonded to one surface of the substrate obtained above to produce a first intermediate laminate with a release film (in other words, a support sheet with a release film). The exposed surface of the film-like adhesive obtained above, opposite the side having the release film, was bonded to the exposed surface of the intermediate layer obtained above, opposite the side having the release film, to produce a second intermediate laminate with a release film (a laminate of a release film, an intermediate layer, a film-like adhesive and a release film).

[0356] Next, this second intermediate laminate with release film was punched out using a cutting blade from the release film on the intermediate layer side to the film-like adhesive, and unnecessary portions were removed to produce a second intermediate laminate with release film, which was composed of a film-like adhesive (thickness 7 μm) with a circular planar shape (diameter 305 mm), an intermediate layer (thickness 20 μm), and a release film laminated in this order in the thickness direction on the release film on the film-like adhesive side.

[0357] Next, the release film was removed from the first intermediate laminate with the release film obtained above to expose one surface of the pressure-sensitive adhesive layer. Furthermore, the circular release film was removed from the second intermediate laminate workpiece with the release film obtained above to expose one surface of the intermediate layer. Next, the newly exposed surface of the adhesive layer in the first intermediate laminate was attached to the newly exposed surface of the intermediate layer in the second intermediate laminate product. The substrate and adhesive layer (i.e., the support sheet) in the laminate thus obtained were punched from the substrate side using a cutting blade (diameter 370 mm) to remove unnecessary portions so that the planar shape of these (the support sheet) was circular (diameter 370 mm) and concentric with the circular film-like adhesive and intermediate layer (diameter 305 mm). As described above, a sheet for manufacturing a semiconductor device with a release film was obtained, in which a base material (thickness: 110 μm), an adhesive layer (thickness: 10 μm), an intermediate layer (thickness: 20 μm), a film-shaped adhesive (thickness: 7 μm), and a release film were laminated in this order in the thickness direction thereof.

[0358] <<Evaluation of Sheet for Manufacturing Semiconductor Device>> <Measurement of H(β)> A liquid material (composition for the first test) containing the ethylene-vinyl acetate copolymer was applied to the release-treated surface of the release film (manufactured by Lintec Corporation, "SP-PET381031") and dried, thereby producing a first test piece in the form of a 10-μm-thick film made of the ethylene-vinyl acetate copolymer. Using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., "NDH7000"), in accordance with JIS K 7136:2000, the haze (H(β)) (%) of the first test piece was measured from the exposed surface side thereof. The results are shown in Table 1.

[0359] <Measurement of H(βα), Calculation of H(βα) - H(β)> A liquid material (composition for the second test) containing the ethylene-vinyl acetate copolymer and epoxy resin (b1)-1 and being uniformly mixed therewith was applied to the release-treated surface of the release film (manufactured by Lintec Corporation, "SP-PET381031") and dried, thereby producing a second test piece in the form of a 10-μm-thick film made of a mixture of the ethylene-vinyl acetate copolymer (100 parts by mass) and epoxy resin (b1)-1 (10 parts by mass). For this second test piece, the haze (H(βα)) (%) was measured in the same manner as in the case of the first test piece described above. Then, H(βα) - H(β) (%) was calculated from the obtained measured values. The results are shown in Table 1.

[0360] <Measurement of H(βγ), Calculation of H(βγ) - H(β)> A liquid (third test composition) containing the ethylene-vinyl acetate copolymer and the amine-based ionic liquid (IL-A2) and uniformly mixed with each other was applied to the release-treated surface of a release film ("SP-PET381031" manufactured by Lintec Corporation) and dried to produce a third test piece in the form of a film having a thickness of 10 μm and consisting of a mixture of ethylene-vinyl acetate copolymer (100 parts by mass) and the amine-based ionic liquid (10 parts by mass). The haze (H(βγ)) (%) of this third test piece was measured in the same manner as in the case of the first test piece. Then, H(βγ)-H(β) (%) was calculated from the obtained measured value. The results are shown in Table 1.

[0361] <Measurement of pick-up force of silicon chip with film adhesive without aging> [Manufacturing groups of silicon chips with film-like adhesive] Using a dicing device (DISCO Corp.'s "DFD6361") and a dicing blade (DISCO Corp.'s "ZH05-SD2000-NI-90-BB"), a blade rotation speed of 50,000 rpm and a blade movement speed of 25 mm / sec were used to form a cut to a depth of 75 μm from one side of a silicon wafer (diameter 150 mm, thickness 350 μm), a so-called half cut. This half cut was performed so that a silicon chip measuring 5 mm x 5 mm was finally obtained. Next, a backgrind tape ("AdwillE-3100TN" manufactured by Lintec Corporation) was applied to the half-cut surface of the silicon wafer. Then, using a backgrinding device ("DGP8761" manufactured by Disco Corporation), the exposed surface of the silicon wafer to which the backgrind tape was not applied was ground until the thickness of the silicon wafer was 30 μm, thereby dividing the silicon wafer and producing a large number of silicon chips (thickness 30 μm) measuring 5 mm×5 mm (in this specification, such a size may be described as "5 mm□"). This resulted in a group of silicon chips in which a large number of silicon chips were aligned and fixed on the backgrind tape.

[0362] Next, the release film was removed from the unaged semiconductor device manufacturing sheet obtained above. Then, using a tape mounter ("Adwill RAD2700" manufactured by Lintec Corporation), this semiconductor device manufacturing sheet was heated to 60°C and attached to the exposed surfaces of all the silicon chips in the silicon chip group by the film-like adhesive therein. Furthermore, after that, the backgrind tape was removed from all the silicon chips. As a result, a laminate (a laminate in which the laminate sheet, the film-like adhesive, and the silicon chip group are laminated in this order in the thickness direction) was obtained.

[0363] Next, the film-like adhesive was cut by expanding it using an expander (Disco Corporation "DDS2300") according to the following procedure. That is, first, the laminate was placed on a table. At this time, the base material in the laminate was brought into contact with the table. Next, the laminate was fixed by adsorption to the table, and the table was pushed up under conditions of 0°C, an expansion speed of 100 mm / s, and an expansion amount of 10 mm, thereby expanding the laminate in a direction parallel to its surface. In this way, the film-like adhesive was cut. Next, the adsorption and expansion of the laminate was released, and the area near the outer periphery of the film-like adhesive in the laminate was heated to eliminate slack in the film-like adhesive in that area. As a result of the above, a group of silicon chips with film-like adhesive was obtained, in which a large number of silicon chips with film-like adhesive, each of which had a silicon chip and a cut film-like adhesive applied to its back surface, were aligned and fixed on the intermediate layer in the laminated sheet by the film-like adhesive therein.

[0364] [Measurement of pick-up force of silicon chip with film adhesive without aging] Next, a pick-up device (Fasford Technology's "PU100", number of pins: 5) was used to pick up the silicon chips with the film-like adhesive from the group of silicon chips with the film-like adhesive obtained above under conditions of a push-up height of 250 μm and an expansion amount of 4 mm, and the pick-up force at that time was measured. The pick-up force was measured at 30 points, and the average of these measured values ​​was used as the pick-up force (mN / 5 mm□) of the silicon chips with the film-like adhesive without aging. The results are shown in Table 1.

[0365] <Measurement of pick-up force of silicon chip with film adhesive over time> The sheet for manufacturing a semiconductor device obtained above was left to stand in an environment of 40° C. for one week to allow it to age. Then, the pick-up force of the silicon chip with the film-like adhesive after aging was measured in the same manner as in the measurement of the pick-up force without aging, except that the aged sheet was used instead of the unaged sheet. The results are shown in Table 1.

[0366] <Measurement of surface resistivity of film adhesive without aging> The release film was removed from the semiconductor device manufacturing sheet obtained above, and the entire exposed surface of the resulting film-like adhesive was attached to the adhesive surface of an adhesive tape having a polyethylene terephthalate layer ("PET50(A) PL Shin 8LK" manufactured by Lintec Corporation). The obtained product was then cut into a size of 100 mm x 100 mm, and the laminate of the adhesive tape and the film-like adhesive was peeled off from the intermediate layer to obtain a test piece. The test piece was left to stand for 24 hours in an environment of a temperature of 23°C and a relative humidity of 50% to adjust the humidity, and then the surface resistivity of the exposed surface of the film-like adhesive (the surface that was on the intermediate layer side) was measured. The surface resistivity was measured using a DIGITAL ELECTROMETER (manufactured by ADVANTEST Co., Ltd.) with an applied voltage of 100 V. The results are shown in Table 1.

[0367] <Measurement of surface resistivity of film adhesive over time> The sheet for manufacturing a semiconductor device obtained above was left to stand in an environment of 40° C. for one week to allow it to age. The aged surface resistivity of the film-like adhesive was measured in the same manner as in the measurement of the unaged surface resistivity, except that the aged sheet was used instead of the unaged sheet. The results are shown in Table 1.

[0368] <Calculation of silicon concentration on the film adhesive side of the intermediate layer> In the manufacturing process of the above-mentioned semiconductor device manufacturing sheet, the exposed surface of the intermediate layer before being bonded to the adhesive layer was analyzed by XPS to measure the concentrations (atomic %) of carbon (C), oxygen (O), nitrogen (N) and silicon (Si). From the measured values, the percentage of silicon concentration relative to the total concentration of carbon, oxygen, nitrogen and silicon was calculated. The XPS analysis was performed using an X-ray photoelectron spectrometer (ULVAC, "Quantra SXM") under conditions of an irradiation angle of 45°, an X-ray beam diameter of 20 μmφ, and an output of 4.5 W. The results are shown in the "Percentage of element concentration in intermediate layer (%)" column in Table 1, together with the percentages of concentration (%) of other elements.

[0369] <Evaluation of the effect of suppressing the generation of cutting debris during blade dicing> [Manufacturing groups of silicon chips with film-like adhesive] The release film was removed from the sheet for manufacturing a semiconductor device obtained above. A silicon wafer (diameter 300 mm, thickness 75 μm) whose back surface had been ground with a dry polish finish was used, and the above-mentioned sheet for manufacturing semiconductor device was attached to the back surface (ground surface) of the wafer using a tape mounter ("Adwill RAD2500" manufactured by Lintec Corporation) with the film-like adhesive while heating to 60° C. This resulted in a laminate (a laminate consisting of the laminate sheet, the film-like adhesive, and the silicon wafer, stacked in this order in the thickness direction) consisting of the substrate, the adhesive layer, the intermediate layer, the film-like adhesive, and the silicon wafer.

[0370] Next, the area (the non-laminated area) near the periphery of the first surface of the pressure-sensitive adhesive layer in the laminate where no intermediate layer was provided was fixed to a ring frame for wafer dicing. Next, the silicon wafer was divided by dicing using a dicing device (DISCO Corporation's "DFD6361"), and the film-like adhesive was also cut to obtain silicon chips measuring 8 mm x 8 mm. The dicing was performed by setting the blade rotation speed to 30,000 rpm and the blade movement speed to 30 mm / sec, and cutting the semiconductor device manufacturing sheet from the surface of the film-like adhesive attached to the silicon wafer to the intermediate region of the intermediate layer (i.e., the entire region of the film-like adhesive in the thickness direction and the intermediate layer from the surface of the film-like adhesive side to the intermediate region). The blade used was DISCO Corporation's "Z05-SD2000-D1-90 CC." As a result of the above, a group of silicon chips with film-like adhesive was obtained, in which a large number of silicon chips with film-like adhesive, each of which had a silicon chip and a cut film-like adhesive applied to its back surface, were aligned and fixed on the intermediate layer in the laminated sheet by the film-like adhesive therein.

[0371] [Evaluation of the effect of suppressing the generation of cutting chips] Using a digital microscope (Keyence Corp. "VH-Z100"), the silicon chips with film-like adhesive obtained above were observed from above the silicon chip side to check for the presence or absence of cutting debris. If no cutting debris was generated at all, it was judged as "A", and if even a small amount of cutting debris was generated, it was judged as "B". The results are shown in Table 1.

[0372] <Evaluation of cuttability of film adhesive during expansion> [Manufacturing groups of silicon chips with film-like adhesive] A silicon wafer having a circular planar shape, a diameter of 300 mm, and a thickness of 775 μm was used, and a backgrind tape ("Adwill E-3100TN" manufactured by Lintec Corporation) was attached to one surface of the wafer. Next, a laser beam was irradiated using a laser beam irradiation device (DISCO Corporation, "DFL73161") so as to be focused on a focal point set inside the silicon wafer, thereby forming a modified layer inside the silicon wafer. At this time, the focal point was set so that a large number of silicon chips measuring 8 mm x 8 mm were obtained from the silicon wafer. The laser beam was irradiated from the other side of the silicon wafer (the side on which the backgrind tape was not attached). Next, the other surface of the silicon wafer was ground with a grinder to a thickness of 30 μm, and the grinding force applied to the silicon wafer at this time was used to divide the silicon wafer at the portion where the modified layer was formed, to produce a plurality of silicon chips. As a result, a group of silicon chips was obtained in which a plurality of silicon chips were aligned and fixed on the backgrind tape.

[0373] Next, using a tape mounter ("Adwill RAD2500" manufactured by Lintec Corporation), one of the semiconductor device manufacturing sheets obtained above was heated to 60°C and the film-like adhesive contained therein was attached to the other surface (in other words, the ground surface) of all of the silicon chips (silicon chip group). Next, the area (the non-laminated area) near the periphery where no intermediate layer was provided on the first surface of the adhesive layer in the semiconductor device manufacturing sheet after it had been attached to the group of silicon chips was fixed to a ring frame for wafer dicing.

[0374] Next, the backgrind tape was removed from the group of silicon chips in this fixed state. Then, using a fully automatic die separator (Disco's "DDS2300"), the sheet for manufacturing semiconductor device (film-like adhesive) was cooled in an environment of 0°C while expanding in a direction parallel to its surface, thereby cutting the film-like adhesive along the periphery of the silicon chip. At this time, the peripheral portion of the sheet for manufacturing semiconductor device was fixed, and the entire area where the intermediate layer and the film-like adhesive of the sheet for manufacturing semiconductor device were laminated was pushed up by a height of 15 mm from the substrate side, thereby expanding it. This resulted in a group of silicon chips with film-like adhesive, in which a plurality of silicon chips with film-like adhesive, each of which had a silicon chip and a cut film-like adhesive applied to the other surface (ground surface) of the silicon chip, were aligned and fixed on the intermediate layer.

[0375] Next, the sheet for manufacturing semiconductor device was once released from expansion, and then the laminate (i.e., the laminate sheet) consisting of the base material, the adhesive layer, and the intermediate layer was expanded in a direction parallel to the first surface of the adhesive layer at room temperature. Furthermore, while maintaining this expanded state, the peripheral portion of the laminate sheet on which the silicon chip with the film-like adhesive was not placed was heated. As a result, the kerf width between adjacent silicon chips on the laminate sheet was maintained at a certain value or more while the peripheral portion was contracted.

[0376] [Evaluation of the cuttability of film adhesives] During the manufacturing of the silicon chip group with the film-like adhesive described above, a digital microscope (Keyence Corporation's "VH-Z100") was used to observe the silicon chip group with the film-like adhesive obtained above from above the silicon chip side. Then, among the multiple cut lines of the film-like adhesive extending in one direction that should be formed if the film-like adhesive is normally cut by expanding the semiconductor device manufacturing sheet (film-like adhesive), and the multiple cut lines of the film-like adhesive extending in a direction perpendicular to this direction, the number of cut lines that were not actually formed and the number of cut lines that were incompletely formed were confirmed, and the cuttability of the film-like adhesive was evaluated according to the following evaluation criteria. The results are shown in Table 1. (Evaluation Criteria) A: The total number of cut lines in the film-like adhesive that are not actually formed and cut lines in the film-like adhesive that are incompletely formed is 5 or less. B: The total number of cut lines in the film-like adhesive that are not actually formed and cut lines in the film-like adhesive that are incompletely formed is 6 or more.

[0377] <Evaluation of pick-up ability of silicon chip with film-like adhesive after expansion> After the evaluation of the cutting ability of the film-like adhesive, the silicon chips with the film-like adhesive were picked up from the intermediate layer in the laminated sheet using a die bonding device ("PU100" manufactured by Fasford Technology) with a push-up height of 250 μm and a push-up speed of 5 mm / s. If all the silicon chips with the film-like adhesive could be picked up normally under the condition of a push-up time of 500 ms, it was evaluated as "A". If one or more silicon chips with the film-like adhesive could not be picked up normally under the condition of a push-up time of 500 ms, but all the silicon chips with the film-like adhesive could be picked up normally under the condition of a push-up time of 10 s, it was evaluated as "B". If one or more silicon chips with the film-like adhesive could not be picked up normally even under the condition of a push-up time of 10 s, it was evaluated as "C". The results are shown in Table 1.

[0378] <Measurement of T-peel strength between intermediate layer and film-like adhesive> The release film was removed from the sheet for manufacturing a semiconductor device obtained above. The entire exposed surface of the film-like adhesive in the semiconductor device manufacturing sheet thus produced was bonded to the adhesive surface of an adhesive tape having a polyethylene terephthalate layer ("PET50(A) PL Shin 8LK" manufactured by Lintec Corporation), and the resulting laminate was cut into a size of 50 mm x 100 mm to prepare a test specimen. In accordance with JIS K6854-3, the laminate of the substrate, the adhesive layer and the intermediate layer (i.e., the laminate sheet) was peeled off from the laminate of the film-like adhesive and the adhesive tape, so that the test piece was peeled off in a T-shape, and the maximum peel force (mN / 50mm) measured at this time was used as the T-shape peel strength. At this time, the peel speed was 50mm / min. The results are shown in Table 1.

[0379] <<Production and evaluation of sheets for manufacturing semiconductor devices>> [Example 2] A sheet for manufacturing a semiconductor device was manufactured and evaluated in the same manner as in Example 1, except that, when preparing the composition for forming an intermediate layer, the siloxane compound was not added, and the amount of the ethylene-vinyl acetate copolymer used was changed from 15 g to 16.5 g (in other words, the siloxane compound was replaced with the same mass of the ethylene-vinyl acetate copolymer, and only the ethylene-vinyl acetate copolymer was dissolved in tetrahydrofuran). The results are shown in Table 1. In Table 1, a "-" in the column for additives means that the additive was not used.

[0380] [Example 3] A sheet for manufacturing a semiconductor device was manufactured and evaluated in the same manner as in Example 2, except that the ethylene-vinyl acetate copolymer was replaced with the same mass of ethylene-vinyl acetate copolymer (EVA, weight average molecular weight 30,000, content of structural units derived from vinyl acetate 40 mass%) when preparing the composition for forming an intermediate layer. The results are shown in Table 1.

[0381] [Comparative Example 1] A comparative composition for forming an intermediate layer was prepared by mixing and stirring an acrylic resin (acrylic copolymer) dispersion ("Coponyl N2359-6" manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solids concentration 34%) (100 parts by mass) and a polyvalent isocyanate compound ("Coronate L" manufactured by Nippon Polyurethane Industry Co., Ltd., solids concentration 75%) (10 parts by mass) at room temperature. A comparative sheet for manufacturing a semiconductor device was produced and evaluated in the same manner as in Example 1, except that this comparative composition for forming an intermediate layer was used instead of the above-mentioned composition for forming an intermediate layer. The results are shown in Table 1.

[0382] [Comparative Example 2] Except for not preparing the intermediate layer, a comparative semiconductor device manufacturing sheet was produced in the same manner as in Example 1. More specifically, in the manufacturing process of the semiconductor device manufacturing sheet described above in Example 1, the exposed surface of the film-like adhesive having a release film was bonded to the release-treated surface of the release film, not to the exposed surface of the intermediate layer having a release film, to produce a laminate of the release film, film-like adhesive, and release film, rather than the second intermediate laminate with the release film, and this was used in the subsequent steps. Except for this, a comparative semiconductor device manufacturing sheet was produced in the same manner as in Example 1. This comparative sheet for manufacturing a semiconductor device was then evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0383] [Table 1]

[0384] As is clear from the above results, in Examples 1 to 3, no change was observed in the pick-up force of the silicon chip with the film-like adhesive whether the semiconductor device manufacturing sheet was aged or not, and no change was observed in the physical properties of the film-like adhesive even when the semiconductor device manufacturing sheet was aged. This indicates that no clear change occurred in the composition of the film-like adhesive even when the semiconductor device manufacturing sheet was aged. In other words, the film-like adhesive contains epoxy resin (b1)-1 as component (α2) (crosslinking agent (f)-1 is not component (α2)), but its migration to the pressure-sensitive adhesive layer side was suppressed even when the semiconductor device manufacturing sheet was aged.

[0385] Furthermore, in Examples 1 to 3, the surface resistivity of the film-like adhesive was 1.0×10 14 The surface resistance was over Ω / □, and no change in antistatic properties was observed on the surface that was the intermediate layer side of the film-like adhesive even when the sheet for manufacturing semiconductor device was aged. This indicated that no clear change occurred in the composition of the adhesive layer, which is the only layer containing an antistatic agent, even when the sheet for manufacturing semiconductor device was aged. Here, the antistatic properties of the film-like adhesive were confirmed, but it was presumed that even when the antistatic properties of the adhesive layer were confirmed, no effect of aging of the sheet for manufacturing semiconductor device was observed. That is, the adhesive layer contains the amine-based ionic liquid, which is an antistatic agent, as component (γ2), but its migration to the film-like adhesive side was suppressed even when the sheet for manufacturing semiconductor device was aged.

[0386] Thus, it was confirmed that in the semiconductor device manufacturing sheets of Examples 1 to 3, the intermediate layer suppresses the migration of liquid components in the film-like adhesive to the pressure-sensitive adhesive layer side, and suppresses the migration of liquid components in the pressure-sensitive adhesive layer to the film-like adhesive side. In Examples 1 to 3, both H(βα)-H(β) and H(βγ)-H(β) were 8% or more.

[0387] Furthermore, the values ​​of H(βα)-H(β) and H(βγ)-H(β) suggest that in the semiconductor device manufacturing sheets of Examples 1 and 2, the transfer of liquid components between the pressure-sensitive adhesive layer and the film-like adhesive is more strongly suppressed than in the semiconductor device manufacturing sheet of Example 3. In the ethylene-vinyl acetate copolymer which is the main component (non-silicon resin (β1)) of the intermediate layer, the ratio of the mass of structural units derived from vinyl acetate to the total mass of all structural units was 25 mass% in Examples 1 and 2, and 40 mass% in Example 3.

[0388] Furthermore, in Examples 1 to 3, the generation of cutting waste was suppressed during blade dicing, and poor cutting of the film-like adhesive was suppressed during expanding, demonstrating excellent suitability for dividing semiconductor wafers. In Examples 1 to 3, the weight average molecular weight of the ethylene-vinyl acetate copolymer contained as the main component (non-silicon-based resin (β1)) in the intermediate layer in the sheet for manufacturing semiconductor device was 30,000 or less.

[0389] In addition, in Examples 1 to 3, the content of the ethylene-vinyl acetate copolymer in the intermediate layer relative to the total mass of the intermediate layer was 90.9 mass% or more, and the content of the siloxane-based compound relative to the total mass of the intermediate layer was 9.1 mass% or less.

[0390] Furthermore, in Example 1, the pick-up properties of the silicon chip with the film-like adhesive after expansion were also excellent. In Example 1, the T-peel strength between the intermediate layer and the film-like adhesive was 100 mN / 50 mm, which was moderately low, and the silicon concentration ratio of the intermediate layer was 9%, which was moderately high. These evaluation results were consistent with the evaluation results of the pick-up properties of the silicon chip with the film-like adhesive described above. In Examples 2 and 3, the intermediate layer in the sheet for manufacturing a semiconductor device did not contain the siloxane-based compound.

[0391] In Examples 1 to 3, no nitrogen was detected in the XPS analysis of the exposed surface of the intermediate layer.

[0392] In contrast, in Comparative Example 1, the pick-up force of the silicon chip with the film-like adhesive decreased with the aging of the semiconductor device manufacturing sheet, and the physical properties of the film-like adhesive were changed. This indicated that the composition of the film-like adhesive changed significantly with the aging of the semiconductor device manufacturing sheet. In other words, it was presumed that the film-like adhesive contained epoxy resin (b1)-1 as component (α2), but its migration to the pressure-sensitive adhesive layer was not suppressed with the aging of the semiconductor device manufacturing sheet.

[0393] Furthermore, in Comparative Example 1, the surface resistivity of the film-like adhesive decreased with the aging of the semiconductor device manufacturing sheet, and a change in antistatic property was observed on the surface of the film-like adhesive that was the intermediate layer side with the aging of the semiconductor device manufacturing sheet. This indicated that a clear change occurred in the composition of the adhesive layer, which is the only layer containing an antistatic agent, with the aging of the semiconductor device manufacturing sheet. Here, the antistatic property of the film-like adhesive was confirmed, but even when the antistatic property of the adhesive layer was confirmed, it was presumed that the influence of the aging of the semiconductor device manufacturing sheet was recognized. That is, it was presumed that the adhesive layer contains the amine-based ionic liquid, which is an antistatic agent, as the component (γ2), but the migration of the amine-based ionic liquid to the film-like adhesive side was not suppressed with the aging of the semiconductor device manufacturing sheet.

[0394] Thus, in the comparative semiconductor device manufacturing sheet of Comparative Example 1, the intermediate layer did not inhibit the migration of liquid components in the film-like adhesive to the pressure-sensitive adhesive layer side, nor did it inhibit the migration of liquid components in the pressure-sensitive adhesive layer to the film-like adhesive side. In Comparative Example 1, both H(βα)-H(β) and H(βγ)-H(β) were 1%.

[0395] In Comparative Example 2, regardless of whether the semiconductor device manufacturing sheet had aged or not, the silicon chip with the film-like adhesive could not be picked up, and the pick-up force was not measurable. This indicated that a clear change had already occurred in the composition of the film-like adhesive before the semiconductor device manufacturing sheet had aged. In other words, the film-like adhesive contained epoxy resin (b1)-1 as component (α2), but it was presumed that the migration of this to the pressure-sensitive adhesive layer had already occurred before the semiconductor device manufacturing sheet had aged. This was because the semiconductor device manufacturing sheet for comparison in Comparative Example 2 did not have an intermediate layer. In Comparative Example 2, the pick-up properties of the silicon chip with the film-like adhesive after expansion were also poor.

[0396] In Comparative Example 2, not only was it not possible to separate the silicon chip with the film-like adhesive from the intermediate layer and pick it up, but it was also not possible to prepare the test piece for measuring the surface resistivity of the film-like adhesive, and therefore the surface resistivity could not be measured. [Industrial Applicability]

[0397] The present invention can be used in the manufacture of semiconductor devices. [Explanation of symbols]

[0398] 101: Sheet for manufacturing semiconductor device; 11: Base material; 12: Adhesive layer; 13: Intermediate layer; 13a: First surface of intermediate layer; 14: Film-like adhesive

Claims

1. The adhesive tape includes a substrate, a pressure-sensitive adhesive layer, an intermediate layer, and a film-like adhesive, the pressure-sensitive adhesive layer, the intermediate layer, and the film-like adhesive are laminated in this order on the base material, the intermediate layer contains, as a main component, a non-silicon-based resin (β1) having a weight average molecular weight of 20,000 to 100,000; Furthermore, at least the film-like adhesive contains a component (α2) or the pressure-sensitive adhesive layer contains a component (γ2), the component (α2) is liquid at a temperature of 23° C. and does not have a functional group that reacts with the main component contained in the film-like adhesive, the component (γ2) is liquid at a temperature of 23° C. and has no functional group that reacts with a main component contained in the pressure-sensitive adhesive layer; The haze of the first test piece in the form of a film having a thickness of 10 μm and made of the non-silicon-based resin (β1) is H(β), In the case where the film-like adhesive contains the component (α2), when the haze of a film-like second test piece having a thickness of 10 μm and made of a mixture of 100 parts by mass of the non-silicon-based resin (β1) and 10 parts by mass of the component (α2) is H(βα), H(βα) and H(β) can be calculated by the following formula (X1): (X1) H(βα)-H(β)>7% Fulfilling In the case where the pressure-sensitive adhesive layer contains the component (γ2), when the haze of a film-like third test piece having a thickness of 10 μm and made of a mixture of 100 parts by mass of the non-silicon-based resin (β1) and 10 parts by mass of the component (γ2) is H(βγ), H(βγ) and H(β) can be expressed by the following formula (X2): (X2) H(βγ)-H(β)>7% A sheet for manufacturing semiconductor device that satisfies the above requirements.

2. Furthermore, at least the film-like adhesive contains as a main component a component (α1) that is solid at a temperature of 23° C., or the pressure-sensitive adhesive layer contains as a main component a component (γ1) that is solid at a temperature of 23° C., 2. The sheet for manufacturing a semiconductor device according to claim 1, wherein the component (α1) and the component (γ1) are acrylic resins having structural units derived from a (meth)acrylic acid ester.

3. 3. The sheet for manufacturing a semiconductor device according to claim 1 or 2, wherein the intermediate layer contains, as the non-silicon-based resin (β1), one or more selected from the group consisting of ethylene-vinyl acetate copolymers and polyolefins.

4. the intermediate layer contains an ethylene-vinyl acetate copolymer as the non-silicon-based resin (β1), The ethylene-vinyl acetate copolymer has a ratio of the mass of the structural unit derived from vinyl acetate to the total mass of all structural units of 30 mass% or less. The sheet for manufacturing a semiconductor device according to any one of claims 1 to 3.

5. The semiconductor device manufacturing sheet according to any one of claims 1 to 4, wherein the semiconductor device manufacturing sheet is for cutting the film-like adhesive by cooling and expanding the film-like adhesive.

6. A method for producing the sheet for producing semiconductor device according to any one of claims 1 to 5, The manufacturing method is a method for manufacturing a sheet for manufacturing a semiconductor device, which includes either or both of a film-like adhesive preparation step of preparing the film-like adhesive containing the component (α2) and a pressure-sensitive adhesive layer preparation step of preparing the pressure-sensitive adhesive layer containing the component (γ2).

7. A method for producing a semiconductor chip with a film-like adhesive using the sheet for producing a semiconductor device according to any one of claims 1 to 5, The semiconductor chip with a film-like adhesive includes a semiconductor chip and a film-like adhesive provided on a back surface of the semiconductor chip, The manufacturing method includes a step of attaching the film-like adhesive in the sheet for manufacturing a semiconductor device to a back surface of a semiconductor wafer while heating the sheet for manufacturing a semiconductor device; a step of cutting the semiconductor wafer to which the film-like adhesive has been applied from the circuit formation surface side across the entire thickness direction to divide the semiconductor chips, and cutting the semiconductor device manufacturing sheet in the thickness direction from the film-like adhesive side to an area halfway through the intermediate layer to cut the film-like adhesive, but not cutting into the pressure-sensitive adhesive layer, thereby obtaining a group of semiconductor chips with a film-like adhesive in which a plurality of the semiconductor chips with the film-like adhesive are aligned on the intermediate layer; and a step of separating the semiconductor chip with the film-like adhesive from the intermediate layer and picking it up.

8. A method for producing a semiconductor chip with a film-like adhesive using the sheet for producing a semiconductor device according to any one of claims 1 to 5, The semiconductor chip with a film-like adhesive includes a semiconductor chip and a film-like adhesive provided on a back surface of the semiconductor chip, The manufacturing method includes a step of forming a modified layer inside the semiconductor wafer by irradiating a laser beam so as to be focused at a focal point set inside the semiconductor wafer; a step of grinding the back surface of the semiconductor wafer after the modified layer is formed, and dividing the semiconductor wafer at the portion where the modified layer is formed by utilizing a grinding force applied to the semiconductor wafer, thereby obtaining a group of semiconductor chips in a state where a plurality of the semiconductor chips are aligned; a step of attaching the film-like adhesive therein to the backsides of all of the semiconductor chips in the group of semiconductor chips while heating the sheet for manufacturing semiconductor device; a step of stretching the semiconductor device manufacturing sheet after being attached to the semiconductor chip in a direction parallel to the surface while cooling, thereby cutting the film-like adhesive along the outer periphery of the semiconductor chip, thereby obtaining a group of semiconductor chips with a film-like adhesive in a state where a plurality of the semiconductor chips with the film-like adhesive are aligned on the intermediate layer; and a step of separating the semiconductor chip with the film-like adhesive from the intermediate layer and picking it up.

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